DE102012007795B3 - New aryl amine-terphenyl compounds useful in an organic semiconductive device, preferably organic LED or a photovoltaic device, preferably solar cell - Google Patents

Abstract

Aryl amine-terphenyl compounds (I) are new. Aryl amine-terphenyl compounds of formula (I) are new. R1 : naphthyl or biphenyl; R2 : 1-10C-alkyl, 1-10C-alkoxy, 1-5C-haloalkyl or 6-12C-aryloxy, where R2 is in o and/or p position to the phenyl ring; R3 : H or 1-5C-alkyl; and n : 1-3. An independent claim is included for an organic semiconductive device comprising at least one layer containing (I). [Image].

Description

The present invention relates to aromatic amine terphenyl compounds and their use in organic semiconductive devices.

As organic semiconducting devices are considered devices that contain at least one organic semiconductor layer. Known organic semiconductor components are, for example, organic light-emitting diodes (OLEDs), field-effect transistors, photodetectors and organic solar cells (OPV), in which organic semiconducting materials are used, for example, as charge transport material or blocking material, preferably as hole conductor or electron blocker.

For example, in organic light-emitting diodes, the property of materials are used to emit light when voltage carriers are formed by the application of a voltage which, when recombined, form excited states, which in turn pass into the ground state with the emission of light. To improve the efficiency of organic light-emitting diodes, these often have, in addition to the actual emission layer, charge transport layers which are responsible for the transport of negative and positive charge carriers into the emission layer. These charge transport layers are classified according to the type of the transported charge carriers in hole conductors and electron conductors. A similar layer structure is also known for photovoltaic devices, such as organic solar cells. Multi-layered organic semiconductive devices can be fabricated by known techniques, such as vacuum evaporation or solution deposition.

A desirable property of organic semiconductive devices is high conductivity. This can be improved, for example, by doping individual layers of the organic semiconducting components. The doping increases the conductivity of the layer and thus overcomes a problem of low carrier mobility.

It is known to change organic semiconductors by doping in their electrical properties, in particular in their electrical conductivity, as is the case with inorganic semiconductors (silicon semiconductors).

In this case, an increase in the initially low conductivity and, depending on the type of dopant used, a change in the Fermi level of the semiconductor is achieved by generating charge carriers in the matrix material. Doping leads to an increase in the conductivity of charge transport layers, as a result of which ohmic losses are reduced and an improved transfer of charge carriers between the contact and the organic layer is achieved. The doping is characterized by a charge transfer from the dopant to an adjacent matrix molecule (n-doping, electron conductivity increased), or by the transfer of an electron from a matrix molecule to a nearby dopant (p-doping, hole conductivity increased). The charge transfer can be incomplete or complete and can be z. B. by the interpretation of vibrational bands from FT-IR measurements.

The conductivity of a thin-film sample can be measured by the so-called two-point method. In this case, contacts made of a conductive material are applied to a substrate, for. As gold or indium tin oxide. Thereafter, the thin film to be examined is applied over a large area on the substrate, so that the contacts are covered by the thin layer. After applying a voltage to the contacts, the current then flowing is measured. From the geometry of the contacts and the layer thickness of the sample results from the thus determined resistance, the conductivity of the thin-film material.

At the operating temperature of a doped-layer device, the conductivity of the doped layer should exceed the conductivity of the undoped layer. For this purpose, the conductivity of the doped layers should be high at room temperature, in particular greater than 1 × 10 ^-8 S / cm, but preferably in the range between 10 ^-6 S / cm and 10 ^-2 S / cm. Undoped layers have conductivities of less than 1 × 10 ^-8 S / cm, usually less than 1 × 10 ^-10 S / cm.

Another essential property of the materials used in a component is their thermal stability. This is of particular importance when the device is manufactured by vacuum vapor deposition.

The temperature stability can be determined by the same method or by the same structure by the (undoped or doped) layer heated gradually and after a rest period, the conductivity is measured. The maximum temperature that the layer can endure without losing the desired semiconductor property is then the temperature just before the conductivity breaks down. For example, a doped layer may be heated on a substrate with two adjacent electrodes, as described above, in 1 ° C increments, with 10 seconds left after each step. Then the conductivity is measured. The conductivity changes with the temperature and abruptly breaks down at a certain temperature. The temperature stability therefore indicates the temperature up to which the conductivity does not abruptly break.

With these methods, it must be ensured that the matrix materials have a sufficiently high purity. Such purities can be achieved by conventional methods, preferably gradient sublimation.

The properties of the various materials involved can be described by the lowest unoccupied molecular orbital (LUMO) energy terms and the highest occupied molecular orbital (HOMO), the synonym: ionization potential.

One method of determining ionization potentials (IP) is ultraviolet photoelectron spectroscopy (UPS). As a rule, ionization potentials are determined for the solid, but it is also possible to measure ionization potentials in the gas phase. Both sizes are distinguished by solid state effects, such as the polarization energy of the holes formed in the photoionization process (Sato, Sat., et al., J. Chem. Soc. Faraday Trans. 2, 77, 1621 (1981)). A typical value for the polarization energy is about 1 eV, but larger deviations may also occur.

The ionization potential refers to the beginning of the photoemission spectrum in the range of high kinetic energies of the photoelectrons, that is, the energy of the weakest bound photoelectrons.

An associated method, inverted photoelectron spectroscopy (IPES), can be used to determine electron affinities (EA). However, this method is less common. Alternatively, solid state _energy levels can be determined by electrochemical measurement of oxidation (E _ox ) and reduction potentials (E _red ) in solution. A suitable method is cyclic voltammetry (CV). Empirical methods for deriving the solid-state ionization potential from an electrochemical oxidation potential are described in the literature (eg, BBW Andrade et al., Org Electron 6, 11 (2005); J. Amer. Chem. Soc. 127, (2005), 7227 .).

No empirical formulas are known for the conversion of reduction potentials into electron affinities. This is due to the difficulty of determining electron affinities. Therefore, a simple rule is often used: IP = 4.8 eV + e · E _ox (vs. ferrocene / ferrocenium) or E _A = 4.8 eV + e · E _red (vs. ferrocene / ferrocenium), where e is the electron charge ( See BW Andrade, Org. Electron. 6, 11 (2005) and Ref. 25-28 therein). In the case that other reference electrodes or redox couples are used for referencing the electrochemical potentials, methods for conversion are known (see AJ Bard, LR Faulkner, "Electrochemical Methods: Fundamentals and Applications", Wiley, 2nd Edition 2000). Information on the influence of a solvent can be found in NG Connelly et al., Chem. Rev. 96, 877 (1996).

It is customary, although not really exact, to use the terms "energy of the HOMO" E (HOMO) or "energy of the LUMO" E (LUMO) synonymously with the terms ionization energy and electron affinity (Koopmans Theorem) in that the ionization potentials and electron affinities are such that a higher value means a stronger binding of an released electron. The energy scale of the molecular orbitals (HOMO, LUMO) is the opposite. Therefore, in a rough approximation: IP = -E (HOMO) and EA = -E (LUMO).

To record a cyclovoltamogram, the substance to be tested is placed in an electrochemical cell with working electrode, counterelectrode and reference electrode together with a conducting salt (eg tetrabutylammonium hexafluorophosphate, TBAPF6) and a solvent (eg dichloromethane (DCM), tetrahydrofuran (THF)). given. Thereafter, a voltage cycle is applied to the working electrode (eg 0.0 V -> 1.6 V -> -2.0 V -> 0.0 V), which is traversed at a feed rate (eg 100 mV / s). Oxidative and reductive processes are noticeable by increasing the current. In the case of reversible processes, there is also a corresponding reductive process for each oxidative process. The Redox potential is calculated from the mean value of the peak peaks. In case of irreversible processes the peakon set is used.

From the EP 2042481 A1 are known aromatic amine terphenyl derivatives that can be used in organic electroluminescent devices.

The EP1995234A1 describes mixtures of p-terphenyl compounds and electrophotographic photoreceptors prepared using these blends.

The matrix materials known from the prior art for use in organic semiconductive components are still able to be improved in terms of their conductivity, their thermal stability and also their processibility from solution.

It is therefore an object of the present invention to overcome the disadvantages of the prior art and to provide materials that lead to improved organic semiconducting devices, which in particular exhibit improved conductivity, are thermally stable and / or also easily from a solution can be processed out. In addition, materials that can be provided in high purity in a simple and cost effective manner are desirable.

It is also an object of the present invention to provide corresponding organic semiconductive devices.

wobei
R¹ ausgewählt ist aus Naphthyl oder Biphenylyl;
R² ausgewählt ist aus C₁-C₁₀-Alkyl, C₁-C₁₀-Alkoxy, C₁-C₅-Halogenalkyl und C₆-C₁₂-Aryloxy und R² in ortho- und/oder para-Position am Phenylring vorliegt,
R³ ausgewählt ist aus H oder C₁-C₅-Alkyl;
n = 1–3 ist.The first object of the invention is achieved by a compound of the formula (I)

in which
R ^{1 is} selected from naphthyl or biphenylyl;
R ^{2 is} selected from C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₅ -haloalkyl and C ₆ -C ₁₂ -aryloxy and R ² in the ortho and / or para position on the phenyl ring is present,
R ^{3 is} selected from H or C ₁ -C ₅ alkyl;
n = 1-3.

Preferred embodiments will be apparent from the dependent claims.

It is preferred that the same named substituents are the same.

It is particularly preferred that R ² = C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₁₂ -aryloxy.

It is preferred that R _{1 is} β-naphthyl or 1,1'-biphenyl-4-yl.

It is also preferred that R ^{2 is} C ₁ -C ₅ -alkyl, preferably methyl, iso-propyl or tert-butyl, C ₁ -C ₃ -alkoxy or phenoxy. R ² = phenoxy is preferred in a thermal vacuum evaporation.

wobei R² aus C₁-C₁₀-Alkyl, C₁-C₁₀-Alkoxy, C₁-C₅-Halogenalkyl und C₆-C₁₂-Aryloxy ausgewählt ist.It is preferably provided that the compound is selected from compounds of the formula (II)

wherein R ^{2 is selected} from C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₁ -C ₅ haloalkyl and C ₆ -C ₁₂ aryloxy.

wobei R⁴ und R⁵ unabhängig ausgewählt sind aus H und R² und alle R⁴ und R⁵ nicht gleichzeitig H sind.It is also preferable for the compound to be selected from compounds of the formula (III)

wherein R ⁴ and R ^{5 are} independently selected from H and R ² and all R ⁴ and R ^{5 are} not H at the same time.

The invention also provides an organic semiconductive device comprising at least one layer containing a compound according to the present invention.

It is preferably provided that the layer containing the compound is doped.

It is also proposed according to the invention that the layer containing the compound according to the invention has at least one doped region, and at least one region which is less doped than the doped region, or is undoped.

Particularly preferred is an organic semiconductive device in which the layer containing the compound is a hole transport layer or emitter layer.

The hole transport layer may be doped or undoped. An undoped hole transport layer containing the compound of the present invention may be disposed in a device between a light emitting or absorbing layer (eg, the emitter layer for an OLED) and a doped hole transport layer. This undoped hole transport layer then constitutes an electron blocker layer.

Finally, it is preferred that the organic semiconducting component is an organic light-emitting diode (OLED) or a photovoltaic component, preferably a solar cell.

Surprisingly, it was found that the compounds proposed according to the invention have a significantly improved conductivity and / or a significantly improved thermal stability compared to already known matrix materials. While the improved conductivity is essential to the performance / efficiency of the organic semiconductive device fabricated therewith, the improved thermal stability results in being able to be purified by sublimation at a high throughput in their manufacture and the compounds of the present invention, on the other hand due to their stability in sublimation can be easily used in the production of the inventive organic semiconductive devices, when its layers are applied by thermal vacuum evaporation.

In addition, it has surprisingly been found that the compounds of the invention can be prepared relatively easily requiring relatively few process steps at a low cost and high purity.

The compounds according to the invention can also be used in a simple manner in the preparation of organic semiconductor components if corresponding layers are produced by deposition from a solution.

Finally, it has been found that these compounds are easier to dope than prior art compounds, resulting in less dopant material being needed. Since a small amount of dopant material is necessary, lower light absorption losses also occur

A preferred alternative of the invention provides that the following layer sequences are present in the component: (i) anode / dopant / HTM; (ii) anode / dopant: HTM; (iii) anode / dopant / dopant: HTM. Also preferred is: (iv) dopant / HTM / EML or (v) dopant / HTM / OAS; (vi) p-doped HTM / EML or (vii) dopant: HTM / OAS. The p-doped HTM is doped with the dopants according to the invention. HTM is the hole transport material ("Hole Transport Material"). EML is the emitting layer of an OLED; OAS stands for "optical absorption layer of a solar cell" (typically a donor-acceptor (D-A) heterojunction). "/" Means that the materials occur in separate layers, in a layer stack, and ":" means that the materials are mixed in one layer, the mixture may or may not be homogeneous.

It is further preferred that the layer sequences (i) - (vii) are final layer sequences.

In another embodiment of the invention, a layer is formed which has a continuous HTM as the matrix material, and additionally has an electrical dopant which is not homogeneously distributed in the layer (in the direction of the layer thickness), furthermore preferably gradients. forms.

Particularly preferred compounds according to the invention are;

It has been found, in particular, that compounds with R ₂ = alkyl show markedly improved conductivity compared to known matrix materials, while compounds with R ₂ = aryloxy were improved in terms of thermal stability.

Further features and advantages of the compounds according to the invention and of the organic semiconductive components will become apparent from the following detailed description of preferred embodiments.

Selection of the dopant

Formel (E1) wobei jedes R₁ unabhängig ausgewählt ist aus Aryl und Heteroaryl, wobei Aryl und Heteroaryl mindestens teilweise, bevorzugt vollständig, mit elektronenarmen Gruppen (Akzeptorgruppen) substituiert sind.Preferred dopants are 3-radial compounds

Formula (E1) wherein each R _{1 is} independently selected from aryl and heteroaryl, wherein aryl and heteroaryl are at least partially, preferably completely, substituted with electron-deficient groups (acceptor groups).

Aryl is preferably phenyl, biphenylyl, α-naphthyl, β-naphthyl, phenantryl or anthracyl.

Heteroaryl is preferably pyridyl, pyrimidyl, triazyl or quinoxalinyl.

Acceptor groups are electron withdrawing groups, preferably selected from fluoro, chloro, bromo, CN, trifluoromethyl or nitro.

The general synthesis is in the patent application EP1988587 under "Representation of oxocarbon, pseudooxocarbon or radial structures" described.

Examples of acceptors useful as p-dopants are: 2,2,7,7-tetrafluoro-2,7-dihydro-1,3,6,8-dioxa-2,7-dibora-pentachloro-benzo [e] pyrene; 1,4,5,8-tetrahydro-1,4,5,8-tetrathia-2,3,6,7-tetracyanoanthrachinon; 1,3,4,5,7,8-Hexafluoronaphtho-2,6-chinontetracyanomethan; 2,2 '- (perfluoronaphthalene-2,6-diylidene) dimalononitrile (d3); 2,2 '- (2,5-dibromo-3,6-difluorcyclohexa-2,5-dien-1,4-diylidene) dimalononitril; 2,2 ', 2''- (cyclopropane-1,2,3-triyliden) tris (2- (2,6-dichloro-3,5-difluoro-4- (trifluoromethyl) phenyl) acetonitrile); 4,4 ', 4''- cyclopropane-1,2,3-triylidentris (cyanomethan-1-yl-1-ylidene) tris (2,3,5,6-tetrafluorobenzonitrile); 2,2 ', 2''- (cyclopropane-1,2,3-triylidene) tris (2- (p-cyanotetrafluorophenyl) acetonitrile) (d1); 2,2 ', 2''- (cyclopropane-1,2,3-triylidene) tris (2- (2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl) acetonitrile) (d2). The document DE 103 57 044 describes the use of quinoids and their derivatives as acceptors in organic semiconductor materials. Other dopants are in US 2008/265216 described.

doping concentration

The dopant is present in a doping concentration of ≦ 1: 1 to the matrix molecule, usually in a doping concentration of 1: 2 or less, preferably 1: 5 or less, more preferably 1:10 or smaller. The doping concentration may be practically limited in the range of 1: 1 to 1: 10,000.

Carrying out the doping

• a) Mischverdampfung im Vakuum mit einer Quelle für das Matrixmaterial und einer für den Dotanden.
• b) Dotierung einer Matrixschicht durch eine Lösung von p-Dotanden mit anschließendem Verdampfen des Lösungsmittels, insbesondere durch thermische Behandlung
• c) Oberflächendotierung einer Matrixmaterialschicht durch eine oberflächlich aufgebrachte Schicht von Dotanden
• d) Herstellung einer Lösung von Matrixmolekülen und Dotanden und anschließende Herstellung einer Schicht aus dieser Lösung mittels konventioneller Methoden wie beispielsweise Verdampfen des Lösungsmittels oder Aufschleudern

The doping of the respective matrix material with the p-dopants to be used according to the invention can be produced by one or a combination of the following processes:

• a) Mixed evaporation in vacuum with a source of the matrix material and one for the dopant.
• b) doping of a matrix layer by a solution of p-dopants with subsequent evaporation of the solvent, in particular by thermal treatment
• c) Surface doping of a matrix material layer by a superficially applied layer of dopants
• d) Preparation of a solution of matrix molecules and dopants and subsequent preparation of a layer of this solution by conventional methods such as evaporation of the solvent or spin coating

In this way, according to the invention, it is therefore possible to produce p-doped layers of organic semiconductors which can be used in a variety of ways. Mixed evaporation in vacuum (VTE) is preferred.

Overview of abbreviations occurring only in the examples

• DSC

  - Differential scanning calorimetry

  HPLC

  - High Performance Liquid Chromatography

  MPLC

  Medium pressure liquid chromatography

  TLC

  - Thin Layer Chromatography (Thin Layer Chromatography)

  GC

  - gas chromatography

  NMR

  - Nuclear Magnetic Resonance (Nuclear Magnetic Resonance)

  MTBE

  - methyl tert-butyl ether

  SPS

  - Solvent Purification System

  BINAP

  2,2'-bis (diphenylphosphino) -1,1'-binaphthyl

  UHV

  Ultra-high vacuum

  eq

  Equivalent

The purity data are given exclusively in "area%", that is, calculated as a percentage of the area under the peak of the determinant in proportion to the total area of all peaks integrated in the chromatogram.

Synthesis of the compounds of the invention

Pd(OAc)₂ Palladium(II)acetat C₄H₆O₄Pd 224.508 g/mol BINAP 2,2'-Bis(diphenylphosphino)-1,1'-binaphthalen C₄₄H₃₂P₂ 622.672 g/mol Cs₂CO₃ Cäsiumcarbonat CCs₂O₂ 325.820 g/mol Schema 1. Allgemeines Reaktionsschema zur Synthese der sekundären Amine 1. Synthesis of secondary amines, general procedure

Pd (OAc) ₂ Palladium (II) acetate C ₄ H ₆ O ₄ Pd 224.508 g / mol BINAP 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene C ₄₄ H ₃₂ P ₂ 622,672 g / mol Cs ₂ CO ₃ cesium carbonate CCs ₂ O ₂ 325,820 g / mol Scheme 1. General Reaction scheme for the synthesis of secondary amines

1.1 General Synthesis Instructions

All work was carried out in thoroughly heated glassware in an inert argon atmosphere. Commercially available compounds were used in the purchased purities without additional prepurification steps, except for the solvents which were degassed and dried. A mixture of arylbromide, arylamine, palladium (II) acetate, BINAP and cesium carbonate in abs. Dioxane (dried over sodium, degassed in the argon stream for about 13 minutes) is stirred while refluxing and maintaining an inert atmosphere of argon until the TLC-tracking indicates the almost complete conversion of the amine used in the slight excess. The mixture is then cooled to room temperature, undissolved salts are optionally removed by filtration and the filtrate after addition of methylene chloride (DCM, 100 mL) successively with water (to remove the base), 2 M HCl solution (to remove the excess used Educt amine), saturated aqueous Na ₂ CO ₃ solution (to regenerate the free amine from possibly formed hydrochloride) and again water (for neutralization). After drying the organic phase over MgSO ₄ is evaporated to dryness in vacuo and the residue worked up by gel filtration on silica gel or by flash chromatography on silica gel and optionally by crystallization from DCM / n-hexane and washing processes (eg with boiling Methanol) additionally purified.

1.1.1 Synthesis of N- (p-tolyl) - [1,1'-biphenyl] -4-amine (precursor to (6))

The synthesis was carried out starting from the general procedure. There were added 4-aminobiphenyl (20.78 g, 1.05 eq, 122.8 mmol), palladium (II) acetate (788 mg, 3.0 mol%, 3.5 mmol), BINAP (3.28 g, 4.5 mol%, 5.3 mmol), cesium carbonate ( 53.30 g, 1.4 eq, 163.7 mmol) and 4-bromotoluene (20.00 g, 1 eq, 116.9 mmol) in dioxane (200 mL) at 130 ° C for 3 days. Column chromatographic purification on silica gel (n-hexane / DCM = 1: 1) provided 11 g (36% yield, HPLC purity: 94%) of secondary amine. The product was combined prior to further reaction in the second stage by means of similar pure fractions from other approaches and further purified by recrystallization from boiling methanol (final purity HPLC 99.7%).

1.1.2 Synthesis of N- (p-tolyl) naphthalene-2-amine (precursor to (4))

The synthesis was carried out starting from the general procedure. There were added p-toluidine (10.87 g, 1.05 eq, 101.4 mmol), 2-bromonaphthalene (20.00 g, 96.6 mmol, 1 eq), palladium (II) acetate (651 mg, 2.9 mmol, 3.0 mol%), BINAP ( 2.71 g, 4.4 mmol, 4.5 mol%) and cesium carbonate (44.05 g, 135.2 mmol, 1.4 eq) in dioxane (325 mL) at 130 ° C for 3 days. Column chromatographic purification on silica gel (n-hexane / DCM = 2: 1) provided 17 g (75% yield, HPLC purity:> 99.4%, GC purity: 100%) of secondary amine.

1.1.3 Synthesis of N- (4-methoxyphenyl) - [1,1'-biphenyl] -4-amine (precursor to (7))

The synthesis was carried out starting from the general procedure. P-Anisidine (11.64 g, 1.1 eq, 94.5 mmol), palladium (II) acetate (576 mg, 3.0 mol%, 2.6 mmol), BINAP (2.4 g, 4.5 mol%, 3.9 mmol), cesium carbonate ( 39.1 g, 1.4 eq, 120.0 mmol) and 4-bromobiphenyl (20.00 g, 1 eq, 85.8 mmol) in dioxane (275 mL) at 125 ° C for 4 days. Column chromatographic purification on silica gel (n-hexane / DCM = 1: 1) provided 17.0 g (72% yield, HPLC purity:> 99.1%, GC purity: 100%) of secondary amine.

1.1.4 Synthesis of N- (p-tolyl) naphthalene-1-amine (precursor to (1))

The synthesis was carried out starting from the general procedure. There were added p-toluidine (10.10 g, 1.3 eq, 94.2 mmol), palladium (II) acetate (490 mg, 3.0 mol%, 2.2 mmol), BINAP (2.03 g, 4.5 mol%, 3.3 mmol), cesium carbonate ( 35.40 g, 1.5 eq, 108.7 mmol) and 1-naphthylbromide (15.00 g, 1.0 eq, 72.4 mmol) in dioxane (210 mL) at 125 ° C for 24 hours. Column chromatography on silica gel (n-hexane / DCM = 1: 1) provided 12.7 g (76% yield, HPLC purity: 99.7%, GC purity: 100%) of secondary amine.

1.1.5 Synthesis of N- (4-methoxyphenyl) naphthalene-1-amine (precursor to (2))

The synthesis was carried out starting from the general procedure. There were 1-bromonaphthalene (5.00 g, 24.1 mmol, 1 eq), palladium (II) acetate (160 mg, 0.73 mmol, 3.0 mol%), cesium carbonate (11.80 g, 36.2 mmol, 1.5 eq), BINAP (0.88 g , 1.4 mmol, 4.5 mol%) and p-anisidine (3.86 g, 31.4 mmol, 1.3 eq) in dioxane (100 mL) at 125 ° C for 24 hours. Column chromatographic purification on silica gel (n-hexane / DCM = 1: 1) provided 4.5 g (75% yield, HPLC purity 99.2%, GC purity: 100%) of secondary amine.

1.1.6 Synthesis of N- (4-methoxyphenyl) naphthalene-2-amine (precursor to (5))

The synthesis was carried out starting from the general procedure. There were added 2-bromonaphthalene (5.00 g, 1.2 eq, 24.2 mmol), palladium (II) acetate (136 mg, 3.0 mol%, 0.60 mmol), cesium carbonate (9.18 g, 1.4 eq, 28.2 mmol), BINAP (564 mg , 4.5 mol.%, 0.91 mmol) and p-anisidine (2.48 g, 1.0 eq, 20.1 mmol) in dioxane (100 mL) at 125 ° C for 5 days. Column chromatographic purification on silica gel (n-hexane / DCM = 1: 1) after separation of insoluble salts via filtration without subsequent washing steps yielded 3.3 g (66% yield, HPLC purity> 97.9%, GC purity: 100%) of secondary amine.

1.1.7 Synthesis of N- (4-phenoxyphenyl) - [1,1'-biphenyl] 4-amine (precursor to (13))

The synthesis was carried out starting from the general procedure. There were added 4-bromobiphenyl (5.72 g, 1.0 eq, 24.5 mmol), 4-phenoxyaniline (5.00 g, 1.1 eq, 27.0 mmol), palladium (II) acetate (165 mg, 3.0 mol%, 0.74 mmol), cesium carbonate ( 11.18 g, 1.4 eq, 34.3 mmol) and BINAP (686 mg, 4.5 mol%, 1.1 mmol) in dioxane (80 mL) at 125 ° C for 5 days. Filtration to remove insoluble matter, washing and gel filtration over silica gel (n-hexane / DCM = 1: 2) provided 4.32 g (55% yield, HPLC purity> 99.1%, GC purity 97.8%) of secondary amine.

1.1.8 Synthesis of N - ([1,1'-biphenyl] -4-yl) naphthalene-1-amine (precursor to (8))

The synthesis was carried out starting from the general procedure. There were 4-aminobiphenyl (12.83 g, 75.8 mmol, 1.3 eq), 1-naphthyl bromide (12.07 g, 58.3 mmol, 1.0 eq), palladium (II) acetate (400 mg, 1.8 mmol, 3.0 mol%), cesium carbonate ( 28.50 g, 87.5 mmol, 1.5 eq) and BINAP (1.65 g, 2.6 mmol, 4.5 mol%) in dioxane (210 mL) at 125 ° C overnight. Column chromatographic purification on silica gel (n-hexane / DCM = 1: 1) provided 15.5 g (90% yield, HPLC purity> 99.5%, GC purity 100%) of secondary amine.

1.1.9 Synthesis of N - ([1,1'-biphenyl] -4-yl) naphthalene-2-amine (precursor to (9))

The synthesis was carried out starting from the general procedure. There were 4-aminobiphenyl (15.95 g, 1.3 eq, 94.3 mmol), 2-naphthyl bromide (15.00 g, 1.0 eq, 72.4 mmol), palladium (II) acetate (500 mg, 3.0 mol%, 2.2 mmol), cesium carbonate ( 35.40 g, 1.5 eq, 108.6 mmol) and BINAP (2.05 g, 4.5 mol%, 3.3 mmol) in dioxane (210 mL) were refluxed overnight (T = 125 ° C). After gel filtration on silica gel (DCM) and washing left 24.23 g (113%) of crude product, which were purified by column chromatography on silica gel (n-hexane / DCM = 1: 1). 18.2 g (85% yield, HPLC purity> 99.8%, GC purity 100%) of secondary amine were obtained.

1.1.10 Synthesis of N- (4- (tert-butyl) phenyl) naphthalene-2-amine (precursor to (11))

The synthesis was carried out starting from the general procedure. There were 2-naphthyl bromide (3.00 g, 14.5 mmol, 1.0 eq), palladium (II) acetate (98 mg, 0.44 mmol, 3.0 mol%), cesium carbonate (7.09 g, 21.8 mmol, 1.5 eq), BINAP (0.41 g , 0.65 mmol, 4.5 mol%) and 4- (tert-butyl) aniline (2.69 g, 18.8 mmol, 1.3 eq) in dioxane (80 ml) were refluxed overnight with exclusion of light (T = 125 ° C.). After washing, gel filtration over silica gel (rinsed with DCM / n-hexane = 1: 1) and treatment of the residue obtained from the filtrate in vacuo with n-hexane in an ultrasonic bath 1.83 g (46% yield, HPLC purity 99.4%, GC Purity 100%) secondary amine as a white solid.

1.1.11 Synthesis of N- (4-phenoxyphenyl) naphthalene-2-amine (precursor to (12))

The synthesis was carried out starting from the general procedure. There were 2-bromonaphthalene (3.00 g, 1.0 eq, 14.5 mmol), 4-phenoxyaniline (3.48 g, 1.3 eq, 18.8 mmol), palladium (II) acetate (98 mg, 3.0 mol%, 0.44 mmol), cesium carbonate ( 7.09 g, 1.5 eq, 21.8 mmol) and BINAP (0.48 g, 4.5 mol%, 0.65 mmol) in dioxane (80 mL) overnight (T = 125 ° C). After filtration, washing and gel filtration over silica gel (DCM / n-hexane = 1: 1), 2.8 g of secondary amine (62% yield, HPLC purity: 99.4%, GC purity: 100%) were obtained.

1.1.12 Synthesis of N- (4- (tert-butyl) phenyl) - [1,1'-biphenyl] -4-amine (precursor to (25))

The synthesis was carried out starting from the general procedure. There were added 4-bromobiphenyl (5.00 g, 1.0 eq, 215 mmol), 4- (tert-butyl) aniline (3.84 g, 1.2 eq, 25.7 mmol), palladium (II) acetate (145 mg, 3.0 mol%, 0.65 mmol), cesium carbonate (14.00 g, 2.0 eq, 43.0 mmol) and BINAP (0.60 g (4.5 mol%, 0.96 mmol) in dioxane (65 mL), refluxed for 6 days with exclusion of light (T = 125 ° C.) Silica gel (DCM), washing, trituration with n-hexane and subsequent purification by column chromatography on silica gel (DCM / n-hexane = 1: 2) yielded 2.41 g of diamine (37% yield, HPLC purity 100%, GC purity: 100%). ) as a white solid.

1.1.13 Synthesis of N- (p-tolyl) - [1,1'-biphenyl] -2-amine (precursor to (38))

The synthesis was carried out starting from the general procedure. There were added 2-bromobiphenyl (3.00 g, 1.0 eq, 12.9 mmol), p-toluidine (1.65 g, 1.2 eq, 15.4 mmol), palladium (II) acetate (140 mg, 4.8 mol%, 0.62 mmol), cesium carbonate ( 6.30 g, 1.5 eq, 19.4 mmol) and BINAP (410 mg, 5.1 mol%, 0.66 mmol) in dioxane (65 mL) were refluxed for 5 days (T = 125 ° C). Addition of water, extraction with DCM and removal of methanol-insoluble matter from the residue left after removal of the solvent yielded 4.16 g of crude product. Column chromatographic purification on silica gel (DCM / n-hexane = 1: 5) afforded, in addition to unreacted 2-bromobiphenyl (2.03 g, 68% of the amount used, HPLC purity 98.7%), the desired secondary amine (0.99 g, 30% yield, HPLC Purity 99.7%, GC purity 100%) as a yellow oil with a honey-like consistency.

1.1.14 Synthesis of N- (2,4-dimethylphenyl) - [1,1'-biphenyl] -4-amine (precursor to (17))

The synthesis was carried out starting from the general procedure. 4-Bromobiphenyl (19.95 g, 1.0 eq, 85.6 mmol), 2,4-dimethylaniline (13.48 g, 1.3 eq, 111.3 mmol), palladium (II) acetate (0.59 g, 3.0 mol%, 2.57 mmol), Cesium carbonate (41.80 g, 1.5 eq, 128.4 mmol) and BINAP (2.42 g, 4.5 mol%, 3.85 mmol) in dioxane (210 mL) were refluxed for 88 hours (T = 125 ° C). Gel filtration on silica gel (DCM), washing according to the general procedure and concentration to dryness gave 26.44 g (113% yield) of crude product. Column chromatographic purification on silica gel (DCM / n-hexane = 1: 5) and washing with methanol gave 16.43 g of secondary amine (70% yield, HPLC purity> 99.5%).

1.1.15 Synthesis of N- (2,4-dimethylphenyl) naphthalene-2-amine (precursor to (16))

The synthesis was carried out starting from the general procedure. 2-Bromonaphthalene (5.00 g, 1.0 eq, 24.2 mmol), 2,4-dimethylaniline (3.07 g, 1.05 eq, 25.4 mmol), palladium (II) acetate (163 mg, 3.0 mol%, 0.72 mmol), Cesium carbonate (11.02 g, 1.4 eq, 33.8 mmol) and BINAP (677 mg, 4.5 mol%, 1.09 mmol) in dioxane (50 mL) were refluxed overnight (T 125 ° C). Gel filtration on silica gel (DCM), washing according to the general procedure and concentration to dryness yielded about 7 g (119% yield) of crude product. Column chromatographic purification on silica gel (DCM / n-hexane = 1: 4) provided two fractions of 2.53 g (43% yield, HPLC purity 99.6%) and 2.60 g (44% yield, HPLC purity 97.8%) of secondary amine. The former fraction was reacted further without further purification in the next stage.

1.1.16 Synthesis of N- (4-isopropylphenyl) naphthalene-2-amine (precursor to (10))

The synthesis was carried out starting from the general procedure. There were 2-bromonaphthalene (6.00 g, 1.0 eq, 29.0 mmol), 4-isopropylaniline (3.48 g, 1.3 eq, 37.6 mmol), palladium (II) acetate (195 mg, 3.0 mol%, 0.87 mmol), cesium carbonate ( 14.18 g, 1.5 eq, 43.5 mmol) and BINAP (0.82 g, 4.5 mol%, 1.3 mmol) in dioxane (160 mL) were refluxed for 48 hours (T = 125 ° C). Filtration to remove insoluble matters, washing according to the general procedure and concentration to dryness, followed by silica gel column chromatography (DCM / n-hexane = 1: 1) gave a light gray solid solid product. This was taken up in n-hexane, treated in an ultrasonic bath and isolated by filtration, washed with n-hexane and dried. It was possible to obtain 3.75 g (yield 50%, HPLC purity 99.1%) of secondary amine as a white solid.

1.1.18 Synthesis of N-mesityl [1,1'-biphenyl] -4-amine (precursor to (20))

The synthesis was carried out starting from the general procedure. There were 4-bromobiphenyl (18.75 g, 1.0 eq, 80.5 mmol), 2,4,6-trimethylaniline (14.10 g, 1.3 eq, 104.6 mmol), palladium (II) acetate (0.55 g, 3.0 mol.%, 2.45 mmol ), Cesium carbonate (39.30 g, 1.5 eq, 120.7 mmol) and BINAP (1.75 g, 3.5 mol%, 2.79 mmol) in dioxane (210 mL) for 2 days (T = 125 ° C). Gel filtration on silica gel (DCM), washing according to the general. Synthesis and concentration to dryness yielded 27.5 g (119% yield) of crude product. Column chromatographic purification on silica gel (DCM / n-hexane = 1: 2) and treatment of the isolated fractions with methanol in an ultrasound bath yielded 12.4 g (53% yield, HPLC purity 89%) of secondary amine. Recrystallization from boiling methanol resulted in two fractions of 3 g each (13% yield, HPLC purity 97.7%, GC-MS purity 100%) and 4.9 g (21% yield, HPLC purity 93.3%). The former was further reacted without further purification in the next stage.

1.2 Characterization data

1.2.1 Characterization of N- (p-tolyl) - [1,1'-biphenyl] -4-amine (precursor to (6))

• TLC (reverse phase, MeCN / water = 9: 1): R _f = 12:38
• TLC (silica gel, DCM / n-hexane = 3: 8): R _f = 0.28
• DSC: Melting point: 133 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.31 ppm (s, 3H, Me), 5.79 (s, 1H, NH), 7.04 ("d", J = 8.5 Hz, 2H), 7.07 ("d", J = 8.5 Hz, 2H), 7.11 ("d", J = 8.5 Hz, 2H), 7.28 ("t", J = 7.5 Hz, 1H, biphenyl H- 4 '), 7.40 ("t", J = 7.5 Hz, 2H, biphenyl H-3'), 7.50 ("d", J = 8.5 Hz, 2H), 7.57 ("d", J = 7.5 Hz, 2H , Biphenyl H-2 ').
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.69 (q, CH ₃ ), 117.00 (d), 119.24 (d), 126.58 (d), 126.75 (d) , 128.08 (d), 129.01 (d), 130.13 (d), 131.49 (s), 133.01 (s), 140.36 (s), 141.10 (s), 143.81 (s).

1.2.2 Characterization of N- (p-tolyl) naphthalene-2-amine (precursor to (4))

• TLC (silica gel, DCM / n-hexane = 2: 3): R _f = 0.39
• DSC: Melting point: 101 ° C (onset), non-sublimed material
• ¹ H-NMR (CDCl ₃ referenced to 7.26 ppm, 500.13 MHz): δ [ppm] = 2.36 (s, 3H, Me), 5.78 (br.s, 1H, NH), 7.11 ("d" with detectable splitting, J = 8.5Hz, 2H, tolyl-H), 7.16 ("d", J = 8.5Hz, 2H, tolyl-H), 7.19 ("Dd", J = 8.5 Hz, 2.0 Hz, 1H, H-3), 7.30 ("t" with detectable fine splitting, J = 8.0 Hz, 1H, H-6), 7.39 ("d" J = 2.0 Hz , 1H, H-1), 7.42 ("t" with detectable fine splitting, J = 8.0 Hz, 1H, H-7), 7.64 ("d", J = 8.0 Hz, 1H, H-4 or H-5 or H-8), 7.74 ("d", J = 8.5 Hz, 1H, H-4 or H-5 or H-8), 7.75 ("d", J = 8.5 Hz, 1H, H-4 or H-8). 5 or H-8).
• ¹³ C-NMR (CDCl ₃ referenced to 77.0 ppm, 125.76 MHz): δ [ppm] = 20.71 (q, CH ₃ ), 110.28 (d), 119.32 (d, tolyl-CH), 119.54 (d), 123.14 ( d), 126.33 (d), 126.36 (d), 127.59 (d), 128.85 (s), 129.08 (d), 129.91 (d, tolyl-CH), 131.34 (s), 134.69 (s), 140.05 (s ), 141.66 (s).

Elemental analysis: values C 87.52%, H 6.48%, N 6.06% exp. values C 87.48%, H 6.61%, N 6.01%

1.2.3 Characterization of N- (4-methoxyphenyl) - [1,1'-biphenyl] -4-amine (precursor to (7))

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.18
• DSC: Melting point: 124 ° C (onset), non-sublimed material
• ¹ H-NMR (CDCl ₃ referenced to 7.26 ppm, 500.13 MHz): δ [ppm] = The spectrum indicates a strong dynamic effect. T. greatly widened signals results. 3.82 (br s, 3H, MeO), 5.57 (very broad s, 1H, NH), 6.89 ("d", J = 8.5 Hz, 2H), 6.98 (very broad s, 2H), 7.11 (very broad s , 2H), 7.28 (br, m, triplet-like splitting, 1H, p-Ph), 7.41 ("t" J = 7.5 Hz, 2H, m-Ph), 7.47 (br, s, 2H), 7.55 ( br, d, J = 6.5 Hz, 2H).
• ¹³ C-NMR (CDCl ₃ referenced to 77.0 ppm, 125.76 MHz): δ [ppm] = 55.53 (q, OCH ₃ ), 114.69 (d), 115.73 (d), 122.39 (d), 126.33 (d), 126.37 (d), 127.91 (d), 128.66 (d), 132.41 (s), 135.42 (s), 140.95 (s), 144.56 (s), 155.41 (s, O-linked).

Elemental analysis: values C 82.88%, H 6.22%, N 5.09%, O 5.81%. exp. values C 82.42%, H 6.29%, N 5.13%, O 6.23%.

1.2.4 Characterization of N- (p-tolyl) naphthalene-1-amine (precursor to (1))

• TLC (silica gel, DCM / n-hexane = 1: 4): R _f = 0.39
• DSC: Melt temperature: 77 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] 2.29 (s, 3H, CH ₃ ), 5.98 (br.s, 1H, NH), 6.94 ("d", J = 8.5 Hz, 2H, tolyl), 7.08 ("d", J = 8.5 Hz, 2H, tolyl), 7.26 ("d", J = 7.5 Hz, 1H, naphthyl), 7.35 ("t", J = 7.5 Hz, 1H, naphthyl), 7.45-7.50 (m, 3H, naphthyl), 7.85 ("dd", J = 7.5 Hz, 2.5 Hz, 1H, naphthyl), 7.99 ("d" with detectable splitting, J = 7.5 Hz , 1H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.66 (q, Me), 114.14 (d, naphthyl C-2), 118.79 (d, tolyl), 121.77 (i.e. , Naphthyl), 122.13 (d, naphthyl), 125.74 (d, naphthyl), 126.33 (d, naphthyl), 126.39 (d, naphthyl), 127.28 (s), 128.77 (d, naphthyl), 130.11 (d, tolyl) , 130.85 (s), 135.04 (s), 140.04 (s, N-linked), 142.11 (s, N-linked).

1.2.5 Characterization of N- (4-methoxyphenyl) naphthalene-1-amine (precursor to (2))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.38
• DSC: Melting point: 111 ° C (onset), non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.29 (s, 3H, CH ₃ ), 5.98 (br. S, 1H, NH), 6.94 ("d", J = 8.5Hz, 2H, tolyl), 7.08 ("d", J = 8.5Hz, 2H, tolyl), 7.26 ("d", J = 7.5Hz, 1H, naphthyl), 7.35 ("t", J = 7.5Hz, 1H, naphthyl), 7.45-7.50 (m, 3H, naphthyl), 7.85 ("dd", J = 7.5Hz, 2.5Hz, 1H, naphthyl), 7.99 ("d" with detectable splitting, J = 7.5 Hz, 1H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.66 (q, Me), 114.14 (d, naphthyl C-2), 118.79 (d, tolyl), 121.77 (i.e. , Naphthyl), 122.13 (d, naphthyl), 125.74 (d, naphthyl), 126.33 (d, naphthyl), 126.39 (d, naphthyl), 127.28 (s), 128.77 (d, naphthyl), 130.11 (d, tolyl) , 130.85 (s), 135.04 (s), 140.04 (s, N-linked) 142.11 (s, N-linked).

1.2.6 Characterization of N- (4-methoxyphenyl) naphthalene-2-amine (precursor to (5))

• TLC (silica gel, DCM / n-hexane 1: 1): R _f = 0.60
• DSC: Melting point: 103 ° C (onset), non-sublimed material
• ¹ H-NMR (CDCl ₃ referenced to 7.26 ppm, 500.13 MHz): δ [ppm] = 3.83 (s, 3H, OMe), 5.68 (br.s, 1H, NH), 6.92 ("d" with fine resolution, J = 9.0 Hz, 2H, phenylene), 7.12 ("dd" J = 8.5 Hz, 2.5 Hz, 1H naphthyl H-5 or H-8), 7.17 ("d" with fine splitting, J = 9.0 Hz, 2H, phenylene) , 7.22 ("d" J = 3.0 Hz, 1H, naphthyl H-1), 7.25 ("t" with fine splitting, J = 8.0 Hz, 1H, naphthyl H-6 or H-7), 7.37 ("t" with Fine resolution, J = 8.0 Hz, 1H, naphthyl H-6 or H-7), 7.59 ("d, J = 8.0 Hz, 1H, naphthyl H-3 or H-4), 7.70 (" d ", J = 9.0 Hz, 1H, naphthyl H-5 or H-8), 7.71 ("d", J = 8.0 Hz, 1H, naphthyl H-3 or H-4).
• ¹³ C-NMR (CDCl ₃ referenced to 77.00 ppm, 125.76 MHz): δ [ppm] = 55.56 (q, OMe), 108.76 (d, naphthyl), 114.72 (d, phenylene), 118.86 (d, naphthyl), 122.56 (d, phenylene), 122.84 (d, naphthyl), 126.20 (d, naphthyl), 126.36 (d, naphthyl), 127.59 (d, naphthyl), 128.52 (s), 129.11 (d, naphthyl), 134.77 (s) , 135.47 (s), 142.88 (s, C _Ar -N), 155.52 (s, C _Ar -O).

1.2.7 Characterization of N- (4-phenoxyphenyl) - [1,1'-biphenyl] -4-amine (precursor to (13))

• TLC (silica gel, DCM / n-hexane = 2: 1): R _f = 0.76
• DSC: Melting point: 137 ° C (onset), non-sublimed material
• ¹ H-NMR (CDCl ₃ referenced to 7.26 ppm, 500.13 MHz): δ [ppm] = 5.69 (br.s, 1H, NH), 6.98-7.02 (m, 4H), 7.08 ("t", J = 7.5 Hz, 1H, p-Ph), 7.08 ("d", J = 8.5 Hz, 2H), 7.13 ("dt, J = 9.0 Hz, 2.5 Hz, 2H), 7.30 (" t ", J = 7.5 Hz, 1H, p-Ph), 7.33 ("t" with fine splitting, J = 8.0Hz, 2H, m-Ph), 7.42 ("t", J = 8.0Hz, 2H, m-Ph), 7.51 ("dt" , J = 9.0 Hz, 2.5 Hz, 2H), 7.57 ("dd", J = 8.0 Hz, 1.0 Hz, 2H, o-Ph).
• ¹³ C-NMR (CDCl ₃ referenced to 77.00 ppm, 125.76 MHz): δ [ppm] = 116.83 (br.), 117.98 (d), 120.49, 120.63, 122.68 (d), 126.47 (d), 126.51 (d) , 127.98 (br.), 128.71 (d), 129.65 (d), 133.2 (very wide), 138.4 (very wide), 140.82 (br.), 143.3 (very wide), 151.4 (very wide), 158.08 (s , i-Ph, O-linked). There is apparently a kind of dynamic effect, which results in much widened signals.

1.2.8 Characterization of N - ([1,1'-biphenyl] -4-yl) naphthalene-1-amine (precursor to (8))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.75
• DSC: Melting point: 150 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 6.12 (br. S, 1H, NH), 7.06 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene ), 7.28 ("t", J = 7.5Hz, 1H, p-Ph), 7.39-7.43 (m, 4H, m-Ph, 2 x naphthyl), 7.51 (high symmetry m, 2H, naphthyl), 7.51 ( "D" with fine resolution, J = 8.51-Hz, 2H, phenylene), 7.57 ("dd", J = 8.5 Hz, 1.0 Hz, 2H, o-Ph), 7.60 (m, 1H, naphthyl), 7.89 (m , Doublet-like splitting, 1H, naphthyl), 8.04 (m, doublet-like splitting, 1H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 116.59 (d, naphthyl), 117.60 (d, phenylene), 122.11 (d, naphthyl or p-Ph), 123.43 ( d, naphthyl or p-Ph), 126.03 (d, naphthyl or p-Ph), 126.35 (d, naphthyl or p-Ph), 126.46 (d, naphthyl or p-Ph), 126.63 (d, phenylene), 126.81 (d, naphthyl or p-Ph), 128.12 (d, phenylene), 128.18 (s), 128.80 (d, naphthyl or p-Ph), 129.03 (d, phenylene). 133.29 (s). 135.08 (s), 138.83 (s), 141.10 (s, C _ar -N), 144.73 (s, C _ar -N).

1.2.9 Characterization of N - ([1,1'-biphenyl] -4-yl) naphthalene-2-amine (precursor to (9))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.46
• DSC: Dab point: 146 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 6.08 (br.s, 1H, NH), 7.25 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene ), 7.28-7.32 (m, 3H), 7.39-7.44 (m, 3H), 7.50 ("d" J = 2.0 Hz, 1H, naphthyl H-1), 7.57 ("d" with fine splitting, J = 9.0 Hz , 2H, phenylene), 7.60 ("dd", J = 8.0Hz, 1.0Hz, 2H, o-Ph), 7.67 ("d", J = 8.5Hz, 1H, naphthyl), 7.76 ("t", J = 9.0 Hz, 2H, m-Ph).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 111.75 (d, naphthyl), 118.46 (d, biphenyl), 120.35 (d, naphthyl or p-Ph), 123.82 ( d, naphthyl or p-Ph), 126.71 (d, biphenyl), 126.74 (d, naphthyl or p-Ph), 126.77 (d, naphthyl or p-Ph), 126.96 (d, naphthyl or p-Ph), 127.88 (d, naphthyl or p-Ph), 128.20 (d, biphenyl), 129.07 (d, biphenyl), 129.45 (d, naphthyl or p-Ph), 129.54 (s), 134.19 (s), 134.96 (s), 140.99 (s), 141.00 (s), 142.66 (s, C _Ar -N).

1.2.10 Characterization of N- (4- (tert-butyl) phenyl) naphthalene-2-amine (precursor to (11))

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 12:47
• DSC: Melting point: 77 ° C (onset), non-sublimed material, 2 closely spaced peaks
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.32 (s, 9H, CH ₃ ), 5.92 (br. S, 1H, NH), 7.13 ("d" with Fine splitting, J = 8.5 Hz, 2H, phenylene), 7.19 ("dd", J = 9.0 Hz, 2.0 Hz, 1H, naphthyl H-3 or H-4), 7.26 ("t" with fine splitting, J = 8.0 Hz , 1H, naphthyl H-6 or H-7), 7.34 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene), 7.38 ("t" with fine splitting, J = 8.5 Hz, 1H, naphthyl H-6 or H-7), 7.39 ("d", J = 1.5 Hz, 1H, naphthyl H-1), 7.62 ("d", J = 8.5 Hz, 1H, naphthyl H-5 or H-8), 7.72 ( 2 × "d" superimposed, J = 9.0 Hz, 2H, naphthyl H-3 and / or H-4 and / or H-5 and / or H-8).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] 31.50 (q, Me), 34.41 (s, CMe ₃ ), 110.15 (d, naphthyl), 118.85 (d, phenylene) , 119.87 (d, naphthyl), 123.39 (d, naphthyl), 126.49 (d, phenylene), 126.56 (d, naphthyl), 126.67 (d, naphthyl), 127.84 (d, naphthyl), 129.15 (s), 129.32 ( d, naphthyl), 135.06 (s), 140.32 (s), 141.95 (s), 145.01 (s, C _ar -N).

1.2.11 Characterization of N- (4-phenoxyphenyl) naphthalene-2-amine (precursor to (12))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.35
• DSC: Melting point: 98 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 5.91 (br.s, 1H, NH), 7.00 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene and / or o-Ph), 7.07 ("t", J = 7.5 Hz, 1H, p-Ph), 7.18 (m, coupling pattern unclear due to signal superposition, 1H, naphthyl), 7.19 ("d" with fine splitting, J = 9.0 Hz, 2H, phenylene and / or o-Ph), 7.27 ("td", J = 8.0 Hz, 1.0 Hz, 1H, naphthyl H-6 or H-7), 7.33 ("t" with fine splitting, J = 8.0 Hz, 2H, m-Ph), 7.36 ("d", J = 2.5 Hz, 1H, naphthyl H-1), 7.38 ("td", J = 8.0 Hz, 1.0 Hz, 1H, naphthyl H-6 or H-7), 7.63 ("d", J = 8.0 Hz, 1H, naphthyl), 7.72 ("d", J = 8.0 Hz, 1H, naphthyl), 7.73 ("d", J = 8.5 Hz, 1H , Naphthyl),
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 110.11 (d, naphthyl), 118.25 (d, phenylene), 119.68 (d, naphthyl or p-Ph), 120.78 d, phenylene), 121.07 (d, phenylene), 123.01 (d, naphthyl or p-Ph), 123.49 (d, naphthyl or p-Ph), 126.57 (d, naphthyl or p-Ph), 126.74 (d, naphthyl or p-Ph), 127.86 (d, naphthyl or p-Ph), 129.19 (s), 129.43 (d, naphthyl or p-Ph), 129.98 (d, phenylene), 135.05 (s), 138.86 (s), 142.13 (s, C _Ar - N), 151.82 (s, C _Ar - O), 158.48 (s, C _Ar - O).

1.2.12 Characterization of N- (4- (tert-butyl) phenyl) - [1,1'-biphenyl] -4-amine (precursor to (25))

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.54
• DSC: mp 97 ° C (onset), non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.31 (s, 9H, CH 3), 5.82 (br. S, 1H, NH), 7.08 (br. M, 4H , Phenylene), 7.28 ("t", J = 7.5Hz, 1H, p-Ph), 7.32 ("d", J = 8.5Hz, 2H, phenylene), 7.40 ("t", J = 7.5Hz, 2H , m-Ph), 7.50 ("d", J = 8.5 Hz, 2H, phenylene), 7.57 ("d", J = 7.5 Hz, 2H, o-Ph).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 31.52 (q, Me), 34.39 (s, CMe ₃ ), 117.16 (d, phenylene), 118.61 (d, phenylene ), 126.46 (d), 126.60 (d), 126.78 (d, p-Ph), 128.10 (d), 129.03 (d), 133.11 (s), 140.33 (s), 141.11 (s), 143.65 (s, C _Ar -N) _, 144.79 (s, C _Ar -N).

1.2.13 Characterization of N- (p-tolyl) - [1,1'-biphenyl] -2-amine (precursor to (38))

• TLC (silica gel, DCM / n-hexane = 1: 5): R _f = 0.34
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.27 (s, 3H, Me), 5.58 (br.s, 1H, NH), 6.93 ("d" with fine splitting , J = 8.5 Hz, 2H, phenylene), 6.94 ("dd", J = 7.5 Hz, 1.5 Hz, 1H), 7.06 ("d", J = 8.5 Hz, 2H, phenylene), 7.20 ("t" with Fine splitting, J = 8.0 Hz, 1H, p-Ph), 7.21 ("d", J = 7.5 Hz, 1H), 7.25 ("dd", J = 9.0 Hz, 1.0 Hz, 1H), 7.33-7.38 (m , 1H), 7.42-7.44 (m, 4H).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.69 (q, Me), 116.82 (d, 1C), 119.45 (d, 2C), 120.69 (d, 1C) , 127.69 (d, 1C), 128.51 (d, 1C), 129.20 (d, 2C), 129.60 (d, 2C), 130.09 (d, 2C), 131.09 (d, 1C), 131.27 (s), 131.34 ( s), 139.53 (s), 140.96 (s, C _ar -N), 141.35 (s, C _ar -N). The specified number of carbon atoms in the individual signals was determined on the basis of the respective signal intensities.

1.2.14 Characterization of N- (2,4-dimethylphenyl) - [1,1'-biphenyl] -4-amine (precursor to (17))

• TLC (silica gel, DCM / n-hexane = 1: 5): R _f = 0.25
• DSC: Melting point: 59 ° C (onset), non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.22 (s, 3H, Me), 2.29 (s, 3H, Me), 5.46 (s, 1H, NH), 6.90 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene), 6.98 ("dd", J = 8.0 Hz, 1.5 Hz, 1H, broadened signal, xylene ring), 7.06 (s, 1H, broadened signal, xylene ring , CH (CMe) ₂ ), 7.15 ("d", J = 8.0 Hz, 1H, xylene ring), 7.26 ("t" with fine splitting, J = 7.5 Hz, 1H, p-Ph), 7.39 ("t" with Fine splitting, J = 7.5 Hz, 2H, m-Ph), 7.46 (d "with fine splitting, J = 9.0 Hz, 2H, phenylene), 7.55 (" dd ", J = 8.0 Hz, 1.5 Hz, 2H, o-Ph ).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 17.94 (q, Me), 20.80 (q, Me), 116.38 (d, phenylene or o-Ph or m-Ph ), 121.46 (d, xylene or p-Ph), 126.54 (d, phenylene or o-Ph or m-Ph), 126.64 (d, xylene or p-Ph), 127.56 (d, xylene or p-Ph), 128.05 (d, phenylene or o-Ph or m-Ph), 129.00 (d, phenylene or o-Ph or m-Ph), 130.57 (s), 131.96 (d, xylene or p-Ph), 132.32 (s) , 132.98 (s), 138.24 (s), 141.22 (s, C _ar -N), 144.98 (s, C _ar -N).

1.2.15 Characterization of N- (2,4-dimethylphenyl) naphthalene-2-amine (precursor to (16))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.56
• DSC: no DSC measurement since substance was obtained as oil
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.25 (s, 3H, Me), 2.33 (s, 3H, Me), 5.56 (s, br, 1H, NH ), 7.02 ("dd", J = 8.0 Hz, 1.5 Hz, broadened signal, 1H), 7.06 ("d", J = 2.5 Hz, 1H, naphthyl H-1), 7.10 (br. S, 1H, mH Xylyl), 7.13 ("dd", J = 8.5Hz, 2.5Hz, 1H), 7.21 ("d", J = 8.0Hz, 1H), 7.25 ("ddd", J = 8.0Hz, 7.0Hz, 1.0Hz , 1H, naphthyl H-6 or H-7), 7.36 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz, 1H, naphthyl H-6 or H-7), 7.57 ("d", J = 8.5 Hz, 1H), 7.712 ("d", J = 9.0 Hz, 1H), 7.715 ("d", J = 7.5 Hz, 1H).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 17.94 (q, o-Me), 20.82 (q, p-Me), 109.21 (d), 119.38 (d) , 121.89 (d), 123.03 (d), 126.39 (d), 126.60 (d), 127.60 (d), 127.83 (d), 128.78 (s), 129.23 (d), 130.92 (s), 132.00 (d) , 133.27 (s), 135.18 (s), 138.25 (s, C _ar -N), 143.34 (s, C _ar -N).

1.2.16 Characterization of N- (4-isopropylphenyl) naphthalene-2-amine (precursor to (10))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.46
• DSC: Melting point: 69 ° C (onset), non-sublimated material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.25 (d, ³ J = 7.0 Hz, 6H, Me), 2.89 ("quint", J = 7.8 Hz, 1H , C H Me ₂ ), 5.90 (s, 1H, NH), 7.13 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene), 7.18 ("d", J = 9.0 Hz, 1H, naphthyl), 7.19 ("d" with fine splitting, J = 8.0 Hz, 2H, phenylene), 7.26 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 1H, naphthyl H-6 or H-7), 7.38 (" ddd ", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 1H, naphthyl H-6 or H-7), 7.38 (coupling pattern unclear due to signal overlay, 1H, naphthyl H-1), 7.62 (" d ", J = 8.5 Hz, 1H, naphthyl), 7.72 (2 × d superimposed, J = 9.0 Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 24.23 (q, Me), 33.80 (d, CMe ₂ ), 110.10 (d, naphthyl), 119.35 (d, phenylene ), 119.84 (d, naphthyl), 123.39 (d, naphthyl), 126.57 (d, naphthyl), 126.68 (d, naphthyl), 127.56 (d, phenylene), 127.85 (d, naphthyl), 129.14 (s), 129.33 (d, naphthyl), 135.09 (s), 140.64 (s), 142.05 (s, C _ar -N), 142.85 (CAr-N).

1.2.18 Characterization of N-mesityl [1,1'-biphenyl] -4-amine (precursor to (20))

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.55
• DSC: Melting point: 76 ° C (onset), non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.18 (s, 6H, ortho-Me), 2.30 (s, 3H, para-Me), 5.28 (br , 1H, NH), 6.53 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene), 6.96 (s, 2H, mesityl-CH), 7.23 ("t" with fine splitting, J = 7.5 Hz, 1H, p-Ph), 7.37 ("t", J = 8.0 Hz, 2H, m-Ph), 7.40 ("d" with fine splitting, J = 8.5 Hz, 2H, phenylene), 7.52 ("dd", J = 8.0 Hz, 1.5 Hz, 2H, o-Ph).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 18.26 (q, ortho-Me), 20.93 (q, para-Me), 113.67 (d), 126.34 (d, p-Ph), 126.40 (d), 128.07 (d), 128.93 (d), 129.45 (d), 130.77 (s), 135.61 (s), 135.94 (s), 136.28 (s), 141.41 (s, C _Ar -N), 146.67 (s, C _ar -N).

2. Coupling of the secondary amines to the terphenyl core, general procedure

Pd (dba) ₂ Bis (dibenzylideneacetone) palldium C ₃₄ H ₃₈ O ₂ Pd 575.0 g / mol PtBu ₃ Tri-tert-butylphosphine C ₁₂ H ₂₇ P 202.32 g / mol KOtBu Potassium tert-butoxide C ₄ M ₉ CO 112.21 g / mol Scheme 2. General reaction scheme for the coupling of secondary amines to the terphenyl core

2.1 General Synthesis Instructions

All work was carried out in thoroughly cleaned glassware in an inert argon atmosphere. Commercially available compounds were used in the purchased purities without additional prepurification steps, except for the solvents which were degassed and dried. Under an argon atmosphere, secondary amine (2.0-2.2 eq), 4,4 "-dibromo-p-terhenyl (1.0 eq ), Tri-tert-butylphosphine (2.0-3.0 mol%), tris (dibenzylideneacetone) dipalladium (0) (2.0 mol%) and potassium tert-butoxide (3.0 eq). The mixture is dissolved in toluene (degassed, SPS quality) and stirred at 80-85 ° C or under reflux (120 ° C) until almost complete conversion of the educt amine (TLC control). After cooling, excess base is separated either by washing with water or by filtration (partly via a layer of silica gel), the product is precipitated by addition of n-hexane and purified by washing with methanol or by column chromatography on silica gel (DCM / n Hexane mixtures). Additional purification is carried out by gradient sublimation.

2.1.1 Synthesis of N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -diphenyl- [1,1 ': 4', 1 "-terphenyl] -4, 4 '' - diamine (3)

The synthesis was carried out according to the general method of synthesis. N-Phenyl-2-naphthylamine (1.24 g, 2.2 eq, 5.7 mmol), 4,4 "-dibromo-p-terphenyl (1.00 g, 1 eq, 2.6 mmol), tri-tert-butylphosphine (16 mg , 3 mol%, 0.077 mmol), bis (dibenzylideneacetone) palladium (30 mg, 2 mol%, 0.052 mmol) and potassium tert-butoxide (869 mg, 3 eq, 7.7 mmol) in toluene (25 mL, SPS Quality) overnight (18 h) at 80 ° C stirred. Filtration and thorough washing with n-hexane and methanol until the colorless filtrate passed through gave 1.5 g (88% yield, HPLC purity 99.7%) of diamine. Further purification was carried out by means of gradient sublimation (sublimation yields 50-87%).

2.1.2 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (6)

The synthesis was carried out according to the general method of synthesis. N- (p -tolyl) - [1,1'-biphenyl] -4-amines (1.47 g, 2.2 eq, 5.7 mmol), 4,4 "-dibromo-p-terphenyl (1.00 g, 1 eq , 2.6 mmol), tri-tert-butylphosphine (16 mg, 3.0 mol%, 0.077 mmol), bis (dibenzylideneacetone) palladium (30 mg, 2.0 mol%, 0.052 mmol) and potassium tert-butoxide (869 mg, 3 eq, 7.7 mmol) in toluene (25 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Filtration and subsequent product precipitation using n-hexane yielded 1.63 g (85% yield, HPLC purity 97%) of diamine. Further purification was carried out by means of gradient sublimation (sublimation yields of 67-74%).

2.1.3 Synthesis of N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4', 1 '' - terphenyl ] -4,4 '' - diamine (4)

The synthesis was carried out according to the general method of synthesis. N- (p-Tolyl) naphthalene-2-amine (3.97 g, 17.0 mmol, 2.2 eq), 4,4 "-dibromo-p-terphenyl (3.00 g, 7.7 mmol, 1.0 eq), tri-tert - butylphosphine (31 mg, 0.16 mmol, 2.0 mol%), tris (dibenzylideneacetone) dipalladium (0) (142 mg, 0.16 mmol, 2.0 mol%) and sodium tert-butoxide (2.23 g, 23.2 mmol, 3.0 eq). in toluene (75 mL, degassed, SPS quality) overnight at 85 ° C stirred. Filtration, product precipitation with n-hexane and purification by column chromatography on silica gel (DCM / n-hexane = 1: 1) yielded 4.13 g (77% yield, HPLC purity 98.3%) of diamine. Further purification was achieved by gradient sublimation (sublimation yield 87%, HPLC purity 99.8%).

2.1.4 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4-methoxyphenyl) - [1,1 ': 4 ', 1'-terphenyl] -4,4 "-diamine (7)

The synthesis was carried out according to the general method of synthesis. N- (4-methoxyphenyl) - [1,1'-biphenyl] -4-amines (4.68 g, 2.2 eq, 17.0 mmol), 4,4 "-dibromo-p-terphenyl (3.00 g, 1 eq , 7.7 mmol), tri-tert-butylphosphine (47 mg, 3.0 mol%, 0.23 mmol), bis (dibenzylideneacetone) palladium (89 mg, 2.0 mol%, 0.16 mmol) and potassium tert-butoxide (2.60 g, 3 eq, 23.2 mmol) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Product precipitation with n-hexane, washing with water and treatment with MTBE / n-hexane in an ultrasound bath yielded 4.52 g (75% yield, HPLC purity 99.7%) of diamine. Attempts to further purify by gradient sublimation failed and resulted in partial decomposition of the compound.

2.1.5 Synthesis of N ⁴ , N ^{4 "} -di (naphthalen-1-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4', 1 '' - terphenyl ] -4,4 '' - diamine (1)

The synthesis was carried out according to the general method of synthesis. There were N- (p-tolyl) naphthalene-1-amines (3.97 g, 2.2 eq, 17.0 mmol), 4,4 "-dibromo-p-terphenyl (3.00 g, 1.0 eq, 7.7 mmol), tri-tert -butylphosphine (47 mg, 3.0 mol%, 0.23 mmol), bis (dibenzylideneacetone) palladium (89 mg, 2.0 mol%, 0.16 mmol) and potassium tert-butoxide (2.60 g, 3.0 eq, 23.2 mmol) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Filtration through Celite ^®, concentration of the filtrate and precipitation from DCM / n-hexane gave 5.24 g (yield 98%, HPLC purity 97.8%) diamine. By column chromatography on silica gel (n-hexane / DCM = 1: 1), the HPLC purity was increased to 99.2%. Further purification was achieved by gradient sublimation (sublimation yield 77%).

2.1.6 Synthesis of N ⁴ , N ^{4 "} -bis (4-methoxyphenyl) -N ⁴ , N ^4" -di (naphthalen-1-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (2)

The synthesis was carried out according to the general method of synthesis. There were N- (4-methoxyphenyl) naphthalene-1-amines (4.24 g, 17.0 mmol, 2.2 eq), 4,4 "-dibromo-p-terphenyl (3.00 g, 7.7 mmol, 1 eq), tri-tert -butylphosphine (47 mg, 0.23 mmol, 3.0 mol%), bis (dibenzylideneacetone) palladium (89 mg, 0.16 mmol, 2.0 mol%) and potassium tert-butoxide (2.60 g, 23.2 mmol, 3.0 eq) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Product precipitation by means of n-hexane, separation by filtration is carried out by column chromatography on silica gel (DCM / n-hexane = 1: 1) provided 4.4 g of product (HPLC purity 98.5%). Since the crude products from several approaches were combined and purified by chromatography, the yield can only be calculated back. This results in a value of 59%. Attempts to further purify by gradient sublimation failed and resulted in partial decomposition of the compound.

2.1.7 Synthesis of N ⁴ , N ^{4 "} -bis (4-methoxyphenyl) -N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (5)

The synthesis was carried out according to the general method of synthesis. There were N- (p-tolyl) naphthalene-2-amines (4.24 g, 17.0 mmol, 2.2 eq), 4,4 "-dibromo-p-terphenyl (3.00 g, 7.7 mmol, 1 eq), tri-tert -butylphosphine (47 mg, 0.23 mmol, 3.0 mol%), bis (dibenzylideneacetone) palladium (89 mg, 0.16 mmol, 2.0 mol%) and potassium tert-butoxide (2.60 g, 23.2 mmol, 3.0 eq) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Product precipitation by means of n-hexane, separation by filtration and purification by column chromatography on silica gel (DCM / n-hexane = 1: 1) yielded 5.3 g of product (HPLC purity 98.6%). Since the crude products from several approaches were combined and purified by chromatography, the yield can only be calculated back. This results in a value of 71%. Attempts to further purify by gradient sublimation failed and resulted in partial decomposition of the compound.

2.1.8 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4-phenoxyphenyl) - [1,1 ': 4 ', 1''- terphenyl] -4.4''- diamine (13)

The synthesis was carried out according to the general method of synthesis. N- (4-phenoxyphenyl) - [1,1'-biphenyl] -4-amine (4.00 g, 2.2 eq, 11.9 mmol), 4,4 "-dibromo-p-terphenyl (2.09 g, 1.0 eq , 5.3 mmol), tri-tert-butylphosphine (33 mg, 3.0 mol%, 0.16 mmol), bis (dibenzylideneacetone) palladium (62 mg, 2.0 mol%, 0.11 mmol) and potassium tert-butoxide (1.82 g, 3.1 eq, 16.2 mmol) in toluene (50 mL, SPS quality) overnight (20 h) at 80 ° C stirred. Gel filtration over silica gel (DCM), concentration in vacuo and washing with methanol yielded 4.77% (98% yield, HPLC purity 99.6%) of diamine. Further purification was achieved by gradient sublimation (sublimation yield 87%, HPLC purity after sublimation> 99.9%).

2.1.9 Synthesis of N ⁴ , N ^{4 '} - Di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4' -di (naphthalen-1-yl) - [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (8)

The synthesis was carried out according to the general method of synthesis. N - ([1,1'-biphenyl] -4-yl) -naphthalene-1-amine (5.02 g, 17.0 mmol, 2.2 eq), 4,4 "-dibromo-p-terphenyl (3.00 g, 7.7 mmol, 1 eq), tri-tert-butylphosphine (47 mg, 0.23 mmol, 3.0 mol%), bis (dibenzylideneacetone) palladium (89 mg, 0.16 mmol, 2.0 mol%) and potassium tert-butoxide (2.60 g , 23.2 mmol, 3.0 eq) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Product precipitation with n-hexane and thorough washing with methanol provided 6.02 g of product (95% yield, HPLC purity> 98.2%). Further purification was achieved by gradient sublimation (sublimation yield 46-73%). The product contained about 1% of the 2-naphthyl constitution isomer.

2.1.10 Synthesis of N ⁴ , N ^{4 ''} - Di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^{4 ''} -di (naphthalen-2-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (9)

The synthesis was carried out according to the general method of synthesis. N - ([1,1'-biphenyl] -4-yl) -naphthalene-2-amine (5.02 g, 17.0 mmol, 2.2 eq), 4,4 "-dibromo-p-terphenyl (3.00 g, 7.7 mmol, 1 eq), tri-tert-butylphosphine (47 mg, 0.23 mmol, 3.0 mol%), bis (dibenzylideneacetone) palladium (89 mg, 0.16 mmol, 2.0 mol%) and potassium tert-butoxide (2.60 g , 23.2 mmol, 3.0 eq) in toluene (75 mL, SPS quality) overnight (18 h) at 80 ° C stirred. Precipitation with n-hexane, thorough washing with methanol and n-hexane and subsequent purification by column chromatography of the residue on silica gel (DCM / n-hexane = 1: 1) yielded 3.86 g of diamine (61% yield, HPLC purity> 97.3%). , Further purification was achieved by gradient sublimation (sublimation yields 63-80%).

2.1.11 Synthesis of N ⁴ , N ^{4 "} -bis (4- (tert-butyl) phenyl) -N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4' , 1 '' - terphenyl] -4,4 '' - diamine (11)

The synthesis was carried out according to the general method of synthesis. There were N- (4- (tert-butyl) phenyl) naphthalene-2-amines (1.50 g, 2.1 eq, 5.4 mmol), 4,4 "-dibromo-p-terphenyl (1.00 g, 1.0 eq, 2.6 mmol ), Tri-tert-butylphosphine (85 mg, 16.0 mol%, 0.42 mmol), bis (dibenzylideneacetone) palladium (30 mg, 2.0 mol%, 0.05 mmol) and potassium tert-butoxide (875 mg, 3.0 eq, 7.8 mmol) in toluene (60 mL, SPS quality) overnight (23 h) at 85 ° C stirred. Addition of chloroform, washing with water and gel filtration through silica gel (chloroform) followed by sonicating the residue recovered from the filtrate afforded 2.72 g (135% yield, HPLC purity 98.0%). Further purification was achieved by gradient sublimation (sublimation yield 76%, HPLC purity: 99.0%).

2.1.12 Synthesis of N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -bis (4-phenoxyphenyl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (12)

The synthesis was carried out according to the general method of synthesis. N- (4-phenoxyphenyl) -naphthalene-2-amine (2.50 g, 2.2 eq, 8.0 mmol), 4,4 "-dibromo-p-terphenyl (1.42 g, 1.0 eq, 3.7 mmol), tri-tert -butylphosphine (22 mg, 3.0 mol%, 0.11 mmol), bis (dibenzylideneacetone) palladium (42 mg, 2.0 mol%, 0.07 mmol) and potassium tert-butoxide (1.23 g, 3.0 eq, 11.0 mmol) in toluene (30 mL, SPS quality) overnight at 80 ° C stirred. Filtration through Celite ^® followed by recrystallization (DCM / n-hexane) of the residue obtained from the filtrate in vacuo provided 2.9 g of crude product (96% yield). Column chromatographic purification on silica gel (gradient chloroform / n-hexane = 1: 4 → 1: 1) finally gave 2.34 g of diamine (yield 75%, HPLC purity 98.6%). Further purification was achieved by gradient sublimation (sublimation yield 82%).

2.1.13 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4- (tert-butyl) phenyl) - [ 1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (25)

The synthesis was carried out according to the general method of synthesis. N- (4- (tert -butyl) phenyl) - [1,1'-biphenyl] -4-amine (2.00 g, 2.2 eq, 6.6 mmol), 4,4 "-dibromo-p-terphenyl ( 1.17 g, 1.0 eq, 3.0 mmol), tri-tert-butylphosphine (18 mg, 3.0 mol%, 0.09 mmol), bis (dibenzylideneacetone) palladium (35 mg, 2.0 mol%, 0.06 mmol) and potassium tert-butoxide (1.02 g, 3.0 eq, 9.1 mmol) in toluene (25 mL, SPS quality) at 80 ° C overnight. Product precipitation with n-hexane, separation via filtration and thorough washing with methanol and with n-hexane and drying yielded 2.7 g of crude product (108% yield). Recrystallization from DCM / n-hexane gave 2.4 g of diamine (yield 97%, HPLC purity 100%). Further purification was achieved by gradient sublimation (sublimation yield 84%, HPLC purity after sublimation> 99.9%).

2.1.14 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -2-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (38)

The synthesis was carried out according to the general method of synthesis. N- (p-Tolyl) - [1,1'-biphenyl] -2-amine (2.49 g, 2.2 eq, 9.6 mmol), 4,4 "-dibromo-p-terphenyl (1.69 g, 1.0 eq , 4.4 mmol), tri-tert-butylphosphine (27 mg, 3.0 mol%, 0.13 mmol), bis (dibenzylideneacetone) palladium (50 mg, 2.0 mol%, 0.09 mmol) and potassium tert-butoxide (1.47 g, 3.0 eq, 13.1 mmol) in toluene (30 mL, SPS quality) at 80 ° C overnight. After concentration and product precipitation with n-hexane, separation via filtration and subsequent rapid gel filtration over silica gel (DCM), 2.84 g of product (89% yield, HPLC purity 99.6%) were obtained. Further purification was achieved by gradient sublimation (sublimation yield 90%).

2.1.15 Synthesis of 2 ', 5'-dimethyl-N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -diphenyl- [1,1': 4 ', 1 '' -terphenyl] -4,4 '' - diamine (41)

The synthesis was carried out according to the general method of synthesis. The dimethyl-substituted dibromoterphenyl was prepared according to a literature procedure (C. Baillie, J. Xiao, Tetrahedron 2004, 60, 4159-4168.). N-phenylnaphthalene-2-amine (1.94 g, 2.0 eq, 8.8 mmol), 4,4 '' - dibromo-2 ', 5'-dimethyl-1,1': 4 ', 1' '- terphenyl ( 1.84 g, 1.0 eq, 4.4 mmol), tri-tert-butylphosphine (27 mg, 3.0 mol%, 0.13 mmol), bis (dibenzylideneacetone) palladium (51 mg, 2.0 mol%, 0.09 mmol) and potassium tert-butoxide ( 1.48 g, 3.0 eq, 13.2 mmol) in toluene (150 mL, SPS quality) for 43½ hours at 80 ° C stirred. After gel filtration, treatment of the residue obtained from the filtrate (2.86 g) with methanol in an ultrasonic bath and drying in a vacuum oven at 40 ° C left 1.31 g of crude product (43% yield, HPLC purity 55.3%). Purification by MPLC (DCM / n-hexane, linear gradient 15% DCM → 35% DCM over 35 min.), Subsequent precipitation by careful evaporation of the methylene chloride and washing with methanol yielded 0.55 g (18% yield, HPLC purity 96.3%). ) of tertiary diamine. Further purification was achieved by gradient sublimation (sublimation yield 49%).

2.1.16 Synthesis of N ⁴ , N ^{4 ''} - Di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^{4 ''} - bis (2,4-dimethylphenyl) - [1,1 ': 4', 1'-terphenyl] -4,4 '' - diamine (17)

The synthesis was carried out according to the general method of synthesis. There were N- (2,4-dimethylphenyl) - [1,1'-biphenyl] -4-amine (2.96 g, 2.1 eq, 10.8 mmol). 4,4 "-dibromo-p-terphenyl (2.00 g, 1.0 eq, 5.2 mmol), tri-tert-butylphosphine (32 mg, 3.0 mol%, 0.16 mmol), bis (dibenzylideneacetone) palladium (60 mg, 2.0 mol.%, 0.10 mmol) and potassium tert-butoxide (1.75 g, 3.0 eq, 15.6 mmol) in toluene (70 mL, SPS quality) for 67 hours at 80 ° C stirred. After gel filtration on silica gel (DCM / n-hexane = 1: 2) and treatment of the residue obtained from the filtrate in vacuo with methanol in an ultrasound bath remained 4.08 g of diamine (quantitative conversion, HPLC purity 99.1%). Further purification was achieved by gradient sublimation (sublimation yield 80%).

2.1.17 Synthesis of N ⁴ , N ^{4 "} -bis (2,4-dimethylphenyl) N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4', 1 '' -terphenyl] -4,4 "-diamine (16)

The synthesis was carried out according to the general method of synthesis. N- (2,4-dimethylphenyl) naphthalene-2-amine (3.11 g, 2.1 eq, 12.6 mmol), 4,4 "-dibromo-p-terphenyl (2.32 g, 1.0 eq, 6.0 mmol), tri tert-butylphosphine (49 mg, 4.0 mol%, 0.24 mmol), palladium (II) acetate (27 mg, 2.0 mol%, 0.12 mmol) and sodium tert-butylate (1.73 g, 3.0 eq, 18.0 mmol) in toluene (30 mL, SPS quality) for 3 hours at 120 ° C (reflux). The reaction mixture was allowed to cool to room temperature overnight, filtered with suction through a frit and the residue was washed successively with n-hexane, methanol and diethyl ether. Column chromatographic purification of the crude product remaining after drying (4.2 g, 97% yield, HPLC purity 97%) yielded 3.44 g (80% yield, HPLC purity 97.5%) of the desired diamine. Further purification was achieved by gradient sublimation (sublimation yield 86%).

2.1.18 Synthesis of N ⁴ , N ^{4 "} -bis (4-isopropylphenyl) -N ⁴ , N ^4" -di (2-halo-2yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (10)

The synthesis was carried out according to the general method of synthesis. N- (4-Isopropylphenyl) naphthalene-2-amine (1.50 g, 2.2 eq, 5.7 mmol), 4,4 "-dibromo-p-terphenyl (1.01 g, 1.0 eq, 2.6 mmol), tri-tert -butylphosphine (16 mg, 3.0 mol%, 0.08 mmol), bis (dibenzylideneacetone) palladium (30 mg, 2.0 mol%, 0.05 mmol) and potassium tert-butoxide (879 mg, 3.0 eq, 7.8 mmol) in toluene (25 mL, SPS quality) overnight at 80 ° C stirred. The reaction mixture was cooled to room temperature and precipitated solid separated by filtration and washed thoroughly with methanol and n-hexane. The residual crude product (4 g) was taken up in DCM / toluene and washed with saturated aqueous brine. Insoluble solid was separated and combined with the residue obtained from concentration of the dried (over MgSO ₄ ) organic phase. There remained 3.5 g (179% yield, HPLC purity> 72%) crude product, which via MPLC chromatographic purification (yielded 2.6 g of product, 133% yield, HPLC purity 93.2%) and subsequent crystallization from DCM / n-hexane and Washing the resulting solid with DCM was purified. It was possible to obtain 1.28 g (66% yield, HPLC purity 89.6%, only a significant 9.2% impurity, presumably unreacted 4,4 "-dibromo-p-terphenyl) of the desired diamine. Further purification was achieved by means of gradient sublimation (sublimation yield 85%), whereby the impurity was almost completely separated off as "forerun" and an HPLC purity of 99.1% could be achieved.

2.1.20 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -dimesityl- [1,1 ': 4', 1 ''-terphenyl]-4,4''- diamine (20)

The synthesis was carried out according to the general method of synthesis. There were N-mesityl [1,1'-biphenyl] -4-amine (3.00 g, 2.2 eq, 10.4 mmol), 4,4 "-dibromo-p-terphenyl (1.84 g, 1.0 eq, 4.7 mmol). , Tri-tert-butylphosphine (29 mg, 3.0 mol%, 0.14 mmol), bis (dibenzylideneacetone) palladium (55 mg, 2.0 mol%, 0.10 mmol) and potassium tert-butoxide (1.59 g, 3.0 eq, 14.2 mmol) in toluene (60 mL, SPS quality) at 80 ° C overnight. Product precipitation with n-hexane, separation by filtration and thorough washing with n-hexane and drying and subsequent purification by column chromatography on silica gel (DCM / n-hexane = 1: 1) yielded 2.7 g (yield 71%, HPLC purity 98.1%) desired diamine. Further purification was achieved by gradient sublimation (sublimation yield 77%, HPLC purity 99.2% after sublimation).

2.1.22 Synthesis of N ⁴ , N ⁴ , N ^{4 '} , N ^4'' tetrakis (4- (tert-butyl) phenyl) - [1,1': 4 ', 1''- terphenyl] -4, 4 '' - diamine (26)

The synthesis was carried out contrary to the general method of synthesis starting from 4,4 '' - diaminoterphenyl, but using the same catalyst system. Under an argon atmosphere, 1-bromo-4- (tert-butyl) benzene (3.60 g, 4.4 eq, 16.9 mmol), 4,4 "-diaminopterphenyl (1.00 g, 1.0 eq, 3.8 mmol), tris tert-butylphosphine (154 mg, 20 mol%, 0.76 mmol), bis (dibenzylideneacetone) palladium (219 mg, 10 mol%, 0.38 mmol) and potassium tert-butoxide (2.56 g, 6.0 eq, 22.8 mmol) in Toluene (100 mL, SPS quality) for 69½ hours at 80 ° C stirred. After cooling, the filtrate was concentrated to dryness in vacuo over a layer of silica gel (rinsing with DCM / n-hexane = 1: 3 until the filtrate passing through remained colorless). The remaining residue (3.34 g light orange solid) was taken up in 400 mL methanol, treated for 15 minutes in an ultrasonic bath and then isolated by filtration. Washing with methanol (2 × 50 ml) and drying in a vacuum oven (at 40 ° C.) overnight yielded 2.91 g (97% yield, HPLC purity 99.4%) of the desired diamine. Further purification was achieved by gradient sublimation (sublimation yield 87%).

2.1.24 Synthesis of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4- (tert-butyl) phenyl) -2 ', 5'-dimethyl- [1,1': 4 ', 1''- terphenyl] -4,4''- diamine (36)

The synthesis was carried out according to the general method of synthesis. The dimethyl-substituted dibromoterphenyl was prepared according to a literature procedure (C. Baillie, J. Xiao, Tetrahedron 2004, 60, 41594168.). There were N- (4- (tert-butyl) phenyl) - [1,1'-biphenyl] -4-amine (2.28 g, 2.1 eq, 7.6 mmol), 4,4 '' - dibromo-2 ', 5 '-dimethyl-1,1': 4 ', 1''- terphenyl (1.50 g, 1.0 eq, 3.6 mmol), tri-tert-butylphosphine (22 mg, 3.0 mol%, 0.11 mmol), bis (dibenzylideneacetone) Palladium (41 mg, 2.0 mol.%, 0.07 mmol) and potassium tert-butoxide (1.21 g, 3.0 eq, 10.8 mmol) in toluene (120 mL, SPS quality) over 22½ hours at 80 ° C stirred. After gel filtration (rinsing with DCM / n-hexane = 1: 2, about 600 mL), treating the residue obtained from the filtrate (3.71 g) with methanol in an ultrasonic bath and drying in a vacuum oven at 40 ° C 2.89 g of crude product (94 % Yield, HPLC purity 53.6%). Purification by column chromatography on silica gel (DCM / n-hexane = 1: 3) yielded two fractions to 610 mg (20% yield, HPLC purity 98.2%). and 600 mg (19% yield, HPLC purity 90.4%) of tertiary diamine. Further purification was achieved by gradient sublimation (sublimation yields 77-78%).

measurement methods

In a standardized conductivity test on the existing test chamber, 50 nm thin organic layers are examined for their conductivity. For this purpose, 25 mm × 25 mm substrates are clamped in a substrate holder and measured during the vapor deposition with organic materials in terms of conductivity of the vapor-deposited layer. The substrate consists of a 1 mm thick quartz glass and is provided with 4 equal ITO patterns. On the substrate holder are 4 gold contacts, via which the contacting takes place to the substrate. The substrates are clamped in the substrate holder and then fed to a high-vacuum chamber (process pressure 1E-6 mbar). Via the non-conductive distance of the ITO contact patterns on the substrate, the organic layer is applied during the evaporation process and measured in situ. This means that at a layer thickness of 0 nm the measurement is started and a DC voltage is applied to the substrate via the described gold contacts. With increasing layer up to 50 nm, the conductivity of the vapor-deposited layer is accordingly recorded and graphically displayed by analysis programs. An extension of this process can be found in the temperature stability study. In this case, the vapor-deposited substrate is supplied to a constant temperature rate. At the same time, the conductivity of the vapor-deposited layer is analyzed. After the conductivity has reached its maximum, a significant collapse of the measured values and the resulting measurement curve can be seen. The temperature in the maximum of the conductivity is called breakdown temperature. The test is finished as soon as this maximum is passed. Afterwards, the vapor-deposited substrate is cooled down. The test is complete as soon as the UHV chamber is vented and the vaporized substrate removed from the vacuum system.

2.2 Characterization data

Conductivity studies were conducted on a variety of compounds of this invention.

For this purpose, the compounds of the invention (1), (4), (6), (10), (11), (16), (17), (20), (25), (36) and (38) while corresponding studies were also carried out for comparative compounds (3), (8), (9), (26), (40), (41) which had the following structures:

A comparison of compounds (25) and (26) shows that although the known terphenyldiamine compound (26) substituted on its nitrogen atoms with four p-tert-butyl-phenyl groups has good conductivity, a combination of R2 = p-tertiary Butyl and R1 = a system with a greater conjugation than phenyl, represented here by 1,1'-biphenyl-4-yl, leads to an even better conductivity than p-tert-butylphenyl itself. The same conclusion is made when comparing compound (11) and compound (26), where R1 = β-naphthyl gives better conductivity. Thus, preferred compounds have on each of their two nitrogens an R2-substituted phenyl containing a conventional conjugated 6π-electron system and an aromatic R1 substituent with a conjugated π-electron system extended as compared to phenyl, the extended conjugation being either by a Condensation of two aromatic rings such. B. in α- or β-naphthyl or by their direct connection such. B. in 1,1'-biphenyl-2-yl or 1,1'-biphenyl-4-yl occurs.

Finally, the advantages according to the invention with regard to improved conductivity are also significant in a comparison, the conductivities for the compounds (3) (not according to the invention) and (4) (according to the invention) or (40) (not according to the invention) and 1 (according to the invention). The compounds according to the invention, with R2 ≠ H, are unexpectedly better than their known.

In a comparison of the conductivity measurement results of the compounds with R1 = biphenylyl (6), (25), (38), (17), and (20), it can be seen that very good conductivities can be achieved with all compounds which have a structure owns the above-mentioned rules. Also, R2 = alkoxy is preferred.

A comparison of compounds (1) and (4) shows that R1 = beta-naphthyl is preferred and gives better results than alpha-naphthyl.

A comparison of compounds (36) and (25) or compounds (41) and (3) shows that R3 = H is preferred. At the same time, however, a comparison of the compounds (36) and (3) shows that the substitution according to the invention on nitrogen atoms is so advantageous that the compounds according to the invention are also better with R 3 ≠ H than compounds according to the invention which do not have R 3 = H.

2.2.1 Characterization of N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -diphenyl- [1,1 ': 4', 1 "-terphenyl] -4, 4 '' - diamine (3)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.68
• CV: HOMO vs. Fc (DCM): 0.41 V (reversible), 2nd oxidation at 0.5 V (rev.) LUMO vs. Fc (THF): -2.85 V (reversible)
• DSC: Melting point: 265 ° C (onset), sublimed material Glass transition temperature Tg: 105 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 7.08 ("t", J = 7.5 Hz, 2H, pH phenyl), 7.17 ("d", J = 8.0 Hz, 4H, oH phenyl), 7.18 ("d" with detectable splitting, J = 8.5 Hz, 4H, terphenyl N-linked ring), 7.30 (m, 6H, mH phenyl, naphthyl H), 7.35 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H-6 or H-7), 7.40 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H-6 or H-7), 7.47 ("d", J = 2.5 Hz, 2H, naphthyl H-1), 7.57 ("d" with apparent splitting, J = 8.5 Hz, 4H, terphenyl N-linked ring), 7.61 ("d", J = 8.0 Hz, 2H, naphthyl H), 7.66 (s, 4H, terphenyl middle ring), 7.75 ("d", J = 8.5 Hz, 2H), 7.77 ("d", J = 8.0 Hz, 2H, naphthyl H) ,
• ¹³ C NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 120.71 (d, naphthyl or p-Ph), 123.57 (d, naphthyl or p-Ph), 124.49 (d, terphenyl or m-Ph or o-Ph), 124.73 (d, naphthyl or p-Ph), 124.86 (d, naphthyl or p-Ph), 124.99 (d, terphenyl or m-Ph or o-Ph), 126.61 (d, Naphthyl or p-Ph), 127.16 (d, naphthyl or p-Ph), 127.18 (d, terphenyl or m-Ph or o-Ph), 127.81 (d, naphthyl or p-Ph), 127.87 (d, terphenyl or m-Ph or o-Ph), 129.19 (d, naphthyl or p-Ph), 129.67 (d, terphenyl or m-Ph or o-Ph), 130.47 (s, naphthyl C-4a), 134.80 (s), 135.04 (s), 139.26 (s), 145.65 (s, N-linked), 147.52 (s, N-linked), 147.93 (s, N-linked).

Elemental analysis: About [%]: C 90.33, H 5.46, N 4.21. exp. [%]: C 90.17, H 5.54, N 4.23. (after sublimation) Conductivities (10 mol%): 2.31E-04 S / cm (d1); 3.21E-06 S / cm (d2); 2.04E-06 S / cm (d3).

2.2.2 Characterization of N ⁴ , N ^{4 '} - di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4' -di-p-tolyl- [1,1 ': 4', '1'-terphenyl] -4,4''- diamine (6)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.73
• CV: HOMO vs. Fc (DCM): 0.41 V (reversible), 2nd oxidation very close to the first LUMO vs. Fc (THF): -2.87 V (reversible)
• DSC: Melting point: no melting peak, even with cyclic measurement Glass transition temperature Tg: 116 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] 2.34 (s, 6H, Me), 7.08 ("d" with detectable fine splitting, J = 8.5 Hz, 4H), 7.14 ( m, 12H), 7.30 ("t", J = 7.5Hz, 2H, H-4'Biphenyl), 7.42 ("t", J = 7.5Hz, 4H, H-3'Biphenyl), 7.50 ("d" with recognizable fine splitting, J = 8.5 Hz, 4H), 7.55 ("d" with detectable fine splitting, J = 8.5 Hz, 4H), 7.58 ("d" with detectable fine splitting, J = 8.5 Hz, 4H), 7.65 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.31 (q, Me), 123.90 (d), 123.96 (d), 125.66 (d), 126.82 (d), 127.11 (d), 127.76 (d), 127.97 (d), 129.06 (d), 130.37 (d), 133.81 (s), 134.55 (s), 135.18 (s), 139.20 (s), 140.86 (s), 145.14 (s), 147.51 (s), 147.54 (s). Based on the signal integration, the signal of the p-Ph carbon of the biphenyl unit is superimposed by the signal at 127.11 ppm.

Elemental analysis: About [%]: C 90.29, H 5.95, N 3.76. exp. [%]: C 90.36, H 5.94, N 3.78. (after sublimation) Conductivities (10 mol.%): 6.03E-04 S / cm (d1); 7.62E-05 S / cm (d2); 1.38E-05 S / cm (d3).

2.2.3 Characterization of N⁴, N^{4 ''}-Di (naphthalen-2-yl) -N⁴, N^{4 ''}- di-p-tolyl- [1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (4)

• TLC (silica gel, DCM / n-hexane = 2: 3): R _f = 0.66
• CV: HOMO vs. Fc (DCM): 0.40 V (reversible) LUMO vs. Fc (THF): -2.85 V (reversible)
• DSC: Melting point: 240 ° C (onset), sublimed material Glass transition temperature Tg: 113 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.34 (s, 6H, Me), 7.08 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.14 ("d", J = 8.0 Hz, 4H, phenylene), 7.16 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.30 ("dd", J = 8.5 Hz, 3.0 Hz, 2H, Naphthyl H-5 or H-8), 7.34 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.39 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.43 ("d", J = 2.0 Hz, 2H, naphthyl H-1), 7.55 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.59 ("d" J = 8.0Hz, 2H, naphthyl), 7.65 (s, 4H, terphenyl middle ring), 7.73 ("d", J = 8.5Hz, 2H, naphthyl), 7.76 (" d ", J = 8.0 Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.91 (q, Me), 119.99 (d, naphthyl), 123.97 (d, terphenyl or phenylene), 124.44 (d, Naphthyl), 124.68 (d, naphthyl), 125.62 (d, terphenyl or phenylene), 126.59 (d, naphthyl), 127.09 (d, naphthyl), 127.12 (d, terphenyl or phenylene), 127.78 (d, terphenyl or phenylene) , 127.80 (d, naphthyl), 129.08 (d, naphthyl), 130.28 (s), 130.38 (d, terphenyl or phenylene), 133.79 (s), 134.62 (s), 134.82 (s), 139.21 (s), 145.27 (s, N-linked), 145.83 (s, N-linked), 147.67 (s, N-linked).

Elemental analysis: values C 90.14%, H 5.82%, N 4.04% exp. values C 90.31%, H 5.95%, N 4.06% Conductivities (10 mol.%): 8.58E-04 S / cm (d1); 7.24E-05 S / cm (d2); 2.53E-05 S / cm (d3).

2.2.4 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4-methoxyphenyl) - [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (7)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.38
• CV: HOMO vs. Fc (DCM): 0.33 V (reversible) LUMO vs, Fc (THF): -2.96 V (irreversible)
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 121 ° C (peak), heating rate 10 K / min, non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 3.81 (s, 6H, MeO), 6.90 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.13 ("d" with fine splitting, J = 9.0 Hz, 8H, phenylene), 7.14 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.30 ("t", J = 7.5 Hz, 2H, p -Ph), 7.41 ("t", J = 7.5 Hz, 4H, m-Ph), 7.50 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene, 7.54 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.58 ("d", J = 7.5Hz, 4H, o-Ph), 7.64 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 55.76 (q, MeO), 115.16 (d), 123.22 (d), 123.27 (d), 126.78 (d), 127.07 (d), 127.70 (d), 127.92 (d), 127.96 (d), 129.05 (d), 134.19 (s), 134.80 (s), 139.19 (s), 140.55 (s), 140.89 (s), 147.65 (s, C _ar -N), 147.68 (s, C _ar -N), 157.00 (s, C _Ar -O). The signal of the p-Ph carbon could not be found due to signal overlays.

Elemental analysis: About [%]: C 86.57 H 5.71 N 3.61 O 4.12 exp. [%]: C 86.08 H 5.95 N 3.52 O not acc.

2.2.5 Characterization of N ⁴ , N ^{4 "} -di (naphthalen-1-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4', 1 '' - terphenyl ] -4,4 '' - diamine (1)

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.54
• CV: HOMO vs. Fc (DCM): 0.40 V (reversible) LUMO vs. Fc (THF): -2.87 V (reversible, not clearly recognizable)
• DSC: Melting point: 235 ° C (onset), sublimed material Glass transition temperature Tg: 123 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CDCl ₃ referenced to 7.26 ppm, 500.13 MHz): δ [ppm] = 2.30 (s, 6H, Me), 7.01 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.04 ( "S", 8H, phenylene), 7.36 ("dd", J = 7.5 Hz, 1.5 Hz, 2H, naphthyl), 7.37 ("ddd", J = 8.5 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H- 3 or H-6 or H-7), 7.44 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.46 ("t", J = 7.5 Hz, 2H, naphthyl H-3, or H- 6 or H-7), 7.48 ("t", J = 7.5 Hz, 2H, naphthyl H-3 or H-6 or H-7), 7.57 (s, 4H, terphenyl middle ring), 7.77 ("d" , J = 8.0 Hz, 2H, naphthyl), 7.89 ("d", J = 8.5 Hz, 2H, naphthyl, 7.98 ("d", J = 8.5 Hz, 2H, naphthyl).
• ¹³ C-NMR (CDCl ₃ referenced to 77.0 ppm, 125.76 MHz): δ [ppm] = 20.74 (q, Me), 120.87 (d), 122.90 (d), 124.30, 126.09, 126.32, 126.34 (d), 126.65 (d), 127.04, 127.31 (d), 128.35, 129.78 (d), 13110 (s), 131.86, 132.94 (s), 135.24 (s), 138.80 (s), 143.54 (s), CN, 145.64 (s , CN), 148.11 (s, CN). A signal was not found due to signal overlays. The assignment of the multiplicities is based on the signal intensities, respectively on the underlying nOe effect.

Elemental analysis: About [%]: C 90.14 H 5.82 N 4.04 exp. [%]: C 90.18 H 5.79 N 4.06 Conductivities (10 mol.%): 3.60E-04 S / cm (d1); 2.13E-05 S / cm (d2); 2.10E-06 S / cm (d3).

2.2.6 Characterization of N ⁴ , N ^{4 "} -bis (4-methoxyphenyl) -N ⁴ , N ^4" -di (naphthalen-1-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (2)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.49
• CV: HOMO vs. Fc (DCM): Measurement not possible, electrodimerization suspected LUMO vs. Fc (THF): -3.09 V (THF reversible)
• DSC: Melting point: 258 ° C (onset), non-sublimed material Glass transition temperature Tg: 109 ° C (onset), heating rate 10 K / min, non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 3.76 (s, 6H, MeO), 6.81 ("d") with fine splitting, J = 9.0 Hz, 4H, phenylene), 6.88 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.11 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.33 ("D", J = 7.5 Hz, 2H, naphthyl), 7.38 ("t" with fine splitting, J = 7.5 Hz, 2H, naphthyl H-6 or H-7), 7.42 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.46 ("t" with fine splitting, J = 8.0 Hz, 2H, naphthyl H-6 or H-7), 7.49 ("t" J = 7.5 Hz, 2H, naphthyl H-3) , 7.56 (s, 4H, terphenyl middle ring), 7.78 ("d", J = 8.0 Hz, 2H, naphthyl), 7.90 ("d", J = 8.0 Hz, 2H, naphthyl), 7.98 ("d", J = 8.5 Hz, 2H, naphthyl).
• ¹³ C-NMR (CDCl ₃ referenced to 77.0 ppm, 125.76 MHz): δ [ppm] = 55.72 (q, MeO), 114.87 (d, anisyl), 119.99 (d, naphthyl, supposed two signals superimposed), 124.48 (i.e. , Naphthyl), 125.74 (d, phenylene), 126.43 (d, naphthyl), 126.56 (d, phenylene), 126.68 (d, naphthyl), 126.83 (d, phenylene), 127.15 (d, naphthyl), 127.47 (d, Phenylene), 128.73 (d, naphthyl), 131.42 (s), 132.45 (s), 135.68 (s), 139.02 (s), 141.48 (s), 143.96 (s, C _ar N), 149.08 (s, C _Ar N), 156.17 (s, _Ar C O).

Elemental analysis: About [%]: C 86.16 H 5.56 N 3.86 exp. [%]: C 84.95 H 5.66 N 3.78

2.2.7 Characterization of N ⁴ , N ^{4 "} -bis (4-methoxyphenyl) -N ⁴ , N ^4" -di (naphthalen-1-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (5)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.50
• CV: HOMO vs. Fc (DCM): 0.33 V (reversible) LUMO vs. Fc (THF): -2.81 V (reversible, not unique)
• DSC: Melting point: 226 ° C (onset), non-sublimed material Glass transition temperature Tg: 118 ° C (onset), heating rate 10 K / min, non-sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 3.81 (s, 6H, OMe), 6.90 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.14 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.15 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.29 ("dd", J = 9.0 Hz, 2.0 Hz, 2H, naphthyl H-3 or H-4), 7.32 ("ddd", J = 8.0Hz, 7.0Hz, 1.0Hz, 2H, naphthyl H-6 or H-7), 7.38 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.39 ("d", J = 2.0 Hz, 2H, naphthyl H-1), 7.54 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.58 ("d", J = 8.0 Hz, 2H, naphthyl H-5 or H-8), 7.65 (s, 4H, terphenyl middle ring), 7.72 ("d", J = 9.0 Hz, 2H, naphthyl H-3 or H-4), 7.75 ("d", J = 8.0 Hz, 2H, naphthyl H-5 or H-8).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] 55.75 (q, Me), 115.16 (d, phenylene), 119.13 (d, naphthyl), 123.30 (d, phenylene), 123.99 (d, naphthyl), 124.51 (d, naphthyl), 126.58 (d, naphthyl), 127.02 (d, naphthyl), 127.07 (d, phenylene), 127.78 (d, naphthyl), 127.88 (d, phenylene), 129.01 (d, naphthyl), 130.07 (s), 134.26 (s), 134.82 (s), 139.18 (s), 140.72 (s), 145.98 (s, C _ar -N), 147.80 (s, C _ar -N) , 156.96 (s, C _Ar -O). The signal assignment to the naphthyl or phenylene units is based solely on the significant intensity differences of the carbon signals.

Elemental analysis: About [%]: C 86.16 H 5.56 N 3.86 O 4.41 exp. [%]: C 86.28 H 5.58 N 3.86 O 4.58

2.2.8 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4-phenoxyphenyl) - [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (13)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.43
• CV: HOMO vs. Fc (DCM): 0.39 V (reversible) LUMO vs. Fc (THF): -2.94 V (reversible)
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 107 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 6.98 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.05 ("dd", J = 8.5 Hz, 1.0 Hz, 4H, o-Ph), 7.11 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph), 7.17 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.18 ("d", with fine splitting, J = 8.0 Hz, 8H, phenylene), 7.31 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph), 7.36 ("t" with fine splitting, J = 8.0 Hz, 4H, m-Ph), 7.42 ("t", J = 7.5 Hz, 4H, m-Ph), 7.52 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.57 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.59 ("dd", J = 8.5 Hz, 1.0 Hz, 4H, o-Ph), 7.66 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 115.82 (d), 120.32 (d), 123.44 (d, p-Ph), 123.86 (d), 123.92 (i.e. ), 126.84 (d), 127.15 (d), 127.84 (d), 128.06 (d), 129.08 (d), 130.06 (d), 134.70 (s), 135.36 (s), 139.21 (s), 140.82 (s ), 143.20 (s), 147.41 (s, C _ar - N), 147.46 (s, C _ar - N), 153.57 (s, C _ar - O), 157.85 (s, C _ar - O). Two carbon signals could not be found due to signal overlay. At least one of these signals is superimposed on the signal at 127.15 ppm based on the significantly higher signal intensity.

Elemental analysis: About [%]: C 87.97 H 5.37 N 3.11 O 3.55 exp. [%]: C 88.01 H 5.46 N 3.15 O not acc. Conductivity (10 mol%): 2.70E-04 S / cm (d1)

2.2.9 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -di (naphthalen-1-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (8)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.60
• CV: HOMO vs. Fc (DCM): 0.42 V (reversible) LUMO vs. Fc (THF): -2.94 V (reversible)
• DSC: Melting point: no melting peak observed, even on cyclic measurement, sublimed material Glass transition temperature Tg: 138 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 7.12 (2 × "d" superimposed, J = 9.0 Hz, 8H, phenylene), 7.28 ("t" with fine splitting, J = 7.5Hz, 2H, p-Ph), 7.40 ("t", J = 7.5Hz, 4H, m-Ph), 7.39-7.42 (m, 4H), 7.46-7.53 (m, 12H), 7.56 ( "Dd", J = 8.5 Hz, 1.0 Hz, 4H, o-Ph), 7.61 (s, 4H, terphenyl middle ring), 7.84 ("d", J = 8.0 Hz, 2H, naphthyl), 7.94 ("d ", J = 8.5 Hz, 2H, naphthyl), 8.00 (" d ", J = 8.5 Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 122.27 (d, phenylene), 122.30 (d, phenylene), 124.35 (d, naphthyl), 126.58 (d, naphthyl or p-Ph), 126.77 (d, phenylene), 126.83 (d, naphthyl or p-Ph), 127.05 (d, phenylene), 127.10 (d, naphthyl or p-Ph), 127.72 (d, phenylene), 127.76 ( d, naphthyl or p-Ph), 127.93 (d, phenylene), 128.81 (d, naphthyl or p-Ph), 129.04 (d, phenylene), 131.59 (s), 134.06 (s), 134.66 (s), 135.74 (s), 139.10 (s), 140.81 (s), 143.44 (s), 147.89 (s, C _ar -N), 147.90 (s, C _ar -N). Two signals could not be found due to signal overlays.

Elemental analysis: About [%]: C 91.14 H 5.43 N 3.43 exp. [%]: C 91.32 H 5.55 N 3.43 Conductivity (10 mol%): 7.31E-05 S / cm (d1)

2.2.10 Characterization of N ⁴ , N ^{4 ''} - Di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^{4 ''} - di (naphthalen-2-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (9)

• TLC (silica gel, DCM / n-hexane = 1: 1): 0.64
• CV: HOMO vs. Fc (DCM): 0.43 V (reversible) LUMO vs. Fc (THF): -2.85 V (reversible)
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 134 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 7.237 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.241 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.32 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph), 7.36 ("dd", J = 9.0 Hz, 2.5 Hz, 2H, naphthyl), 7.37 ( "Ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.41 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.44 ("d" with fine splitting, J = 7.5 Hz, 4H, phenylene), 7.53 ("d", J = 2.0 Hz, 2H, naphthyl H-1), 7.55 ("d" with fine splitting , J = 8.5 Hz, 4H, phenylene), 7.60 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.62 ("t" with fine splitting, J = 7.0 Hz, 4H, m-Ph), 7.64 ("D", J = 8.0 Hz, broad peaks, 2H, naphthyl), 7.68 (s, 4H, terphenyl middle ring), 7.78 ("d", J = 9.0 Hz, 2H, naphthyl), 7.79 ("d" , J = 8.0 Hz, broad peaks, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 1.21.05 (d, naphthyl or p-Ph), 124.73 (d, phenylene), 124.79 (d, phenylene), 124.84 (d, naphthyl or p-Ph), 124.97 (d, naphthyl or p-Ph), 126.66 (d, naphthyl or p-Ph), 126.88 (d, phenylene), 127.19 (d, naphthyl or p-Ph), 127.22 (phenylene), 127.73 (d, naphthyl or p-Ph), 127.83 (d, naphthyl or p-Ph), 127.94 (d, phenylene), 128.14 (d, phenylene), 129.09 (d, phenylene), 129.28, 130.59 (s), 135.93 (s), 140.78 (s), 145.46 (s), 147.27 (s, _Ar C - N), 147.34 (s, _Ar C-N). Some signals could not be found due to its limited solubility due to the low substance concentration in the NMR solvent, even with longer measurement times.

Elemental analysis: About [%]: C 91.1.4 H 5.43 N 3.43 exp. [%]: C 90.21 H 5.62 N 3.47 Conductivity (10 mol%): 1.92E-04 S / cm (d1)

2.2.11 Characterization of N ⁴ , N ^{4 "} -bis (4- (tert-butyl) phenyl) -N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4, 1 '' - terphenyl] -4,4 '' - diamine (11)

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.58
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 133 ° C (onset), already visible before shock cooling, heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.33 (s, 18H, Me), 7.10 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.17 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.30 ("dd", J = 9.0 Hz, 2.0 Hz, 2H, naphthyl), 7.33 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.34 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H-6 or H-7), 7.39 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz , 2H, naphthyl H-6 or H-7), 7.45 ("d", J = 2.5 Hz, 2H, naphthyl H-1), 7.55 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.60 ("d", 8.0 Hz, broadened signal, 2H, naphthyl), 7.66 (s, 4H, terphenyl middle ring), 7.74 ("d", J = 9.0 Hz, 2H, naphthyl), 7.76 ("d", J = 8.5 Hz, broadened signal, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 31.47 (q, Me), 34.57 (s, CMe ₃ ), 120.19 (d, naphthyl), 124.12 (d, phenylene 124.60 (d, naphthyl), 124.69 (d, naphthyl), 124.82 (d, phenylene), 126.56 (d, naphthyl), 126.59 (d, phenylene), 127.08 (d, naphthyl), 127.13 (d, phenylene) , 127.77 (d, phenylene), 127.79 (d, naphthyl), 129.07 (d, naphthyl), 130.32 (s), 134.69 (s), 134.81 (s), 139.24 (s), 145.09 (s), 145.78 (s ), 146.87 (s, C _ar -N), 147.66 (s, C _ar -N).

Elemental analysis: About [%]: C 89.65 H 6.75 N 3.61 exp. [%]: C 89.63 H 6.64 N 3.66 Conductivity (10 mol.%): 6.92E-04 S / cm (d1)

2.2.12 Characterization of N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^{4 '} -bis (4-phenoxyphenyl) - [1,1': 4 ', 1''- terphenyl ] -4,4 '' - diamine (12)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.51
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 100 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] 6.98 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.06 ("d" with fine splitting, J = 8.0 Hz, 4H, o-Ph), 7.10 ("t", J = 7.5 Hz, 2H, p-Ph), 7.17 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.19 ("d With fine splitting, J = 8.5 Hz, 4H, phenylene), 7.33 ("dd", J = 8.5 Hz, 2.0 Hz, 2H, naphthyl), 7.34-7.37 (m, 6H), 7.40 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H-6 or H-7), 7.46 ("d", J = 2.5 Hz, 2H, naphthyl H-1), 7.57 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.62 ("d", J = 8.0 Hz, 2H, naphthyl), 7.66 (s, 4H, terphenyl middle ring), 7.75 ("d", J = 8.5 Hz, 2H, naphthyl) , 7.77 ("d", J = 7.5 Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 118.82 (d, phenylene or o-Ph or m-Ph), 120.00 (d, naphthyl or p-Ph), 120.29 (d, phenylene or o-Ph or m-Ph), 123.43 (d, naphthyl or p-Ph), 123.89 (i.e. , Phenylene or o-Ph or m-Ph), 124.32 (d, naphthyl or p-Ph), 124.76 (d, naphthyl or p-Ph), 126.63 (d, naphthyl or p-Ph), 127.09 (d, phenylene or o-Ph or m-Ph), 127.14 (d, phenylene or o-Ph or m-Ph), 127.80 (d, naphthyl or p-Ph), 127.84 (d, phenylene or o-Ph or m-Ph) , 129.17 (d, naphthyl or p-Ph), 130.05 (d, phenylene or o-Ph or m-Ph), 130.31 (s), 134.75 (s), 134.79 (s), 139.23 (s), 143.32 (s , C _Ar-N), 145.72 (s, _Ar C-N), 147.60 (s, _Ar C-N), 153.56 (s, _Ar C-O), 157.83 (s, _Ar C-O). One of the naphthyl CH signals or the p-Ph carbon is superimposed by other signals.

Elemental analysis: About [%]: C 87.71 H 5.22 N 3.30 O 3.77 exp. [%]: C 87.73 H 5.30 N 3.32 O not acc. Conductivity (10 mol%): 4.42E-04 S / cm (d1)

2.2.13 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4- (tert-butyl) phenyl) - [ 1,1 ': 4', 1 '' - terphenyl] -4,4 '' - diamine (25)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.76
• DSC: melting point: 202 ° C, sublimed material Glass transition temperature Tg: 138 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.33 (s, 18H, Me), 7.10 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.16 ("d" with fine splitting, J = 8.5 Hz, 8H, phenylene), 7.30 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph), 7.34 ("d" with fine splitting, J = 9.0 Hz , 4H, phenylene), 7.42 ("t" with fine splitting, J = 7.5 Hz, 4H, m-Ph), 7.51 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.55 ("d" with Fine splitting, J = 9.0 Hz, 4H, phenylene), 7.59 ("dd", J = 8.0 Hz, 1.5 Hz, 4H, o-Ph), 7.65 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 31.47 (q, Me), 34.56 (s, CMe ₃ ), 124.05 (d), 124.11 (d), 124.92 ( d), 126.59 (d), 126.82 (d), 127.12 (d), 127.75 (d), 127.97 (d), 129.05 (d), 134.63 (s), 135.27 (s), 139.22 (s), 144.96 (d) s), 146.91 (s), 147.48 (s, C _ar -N), 147.52 (s, C _ar -N). The p-phenyl carbon and another aromatic s-carbon are superimposed by other signals.

Elemental analysis: About [%]: C 89.81 H 6.81 N 3.38 exp. [%]: C 89.80 H 6.72 N 3.41 Conductivities (10 mol%): 1.04E-03 S / cm (d1); 4.15E-04 S / cm (d2); 3.37E-05 S / cm (d3).

2.2.14 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -2-yl) -N ⁴ , N ^4" -di-p-tolyl- [1,1 ': 4 ', 1''- terphenyl] -4,4''- diamine (38)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.65
• DSC: Melting point: 280 ° C (onset), sublimed material Glass transition temperature Tg: 90 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 511 ppm, 500.13 MHz): δ [ppm] = 2.22 (s, 6H, Me), 6.76 ("d" with fine resolution, J = 8.5 Hz, 4H, para-phenylene ), 6.85 ("d" with fine splitting, J = 8.5 Hz, 4H, para-phenylene), 6.90 ("d", J = 8.0 Hz, 4H), 7.09-7.15 (m, 6H), 7.22 ("dd" , J = 8.0 Hz, 1.5 Hz, 4H), 7.28-7.39 (m, 12H), 7.53 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.66 (q, Me), 121.39 (d, para-phenylene), 123.21 (d, para-phenylene), 126.19 ( d, ortho-phenylene or p-Ph), 126.80 (d, para-phenylene), 126.98 (d, ortho-phenylene or p-Ph), 127.14 (d, para-phenylene), 128.06 (d, para-phenylene) , 128.81 (d, para-phenylene), 129.07 (d, ortho-phenylene or p-Ph), 129.57 (d, para-phenylene), 129.84 (d, ortho-phenylene or p-Ph), 131.85 (s ), 132.14 (d, ortho-phenylene or p-Ph), 132.79 (s), 139.05 (s), 140.12 (s), 140.80 (s), 144.91 (s, C _ar -N), 145.02 (s, C _Ar -N), 147.76 (s, C _ar -N).

Elemental analysis: About [%]: C 90.29 H 5.95 N 3.76 exp. [%]: C 90.37 H 6.00 N 3.79 Conductivities (10 mol%); 3.28E-04 S / cm (d1); 1.63E-04 S / cm (d2); 3.64E-06 S / cm (d3).

2.2.15 Characterization of 2 ', 5'-dimethyl-N ⁴ , N ^{4 "} -di (naphthalen-2-yl) -N ⁴ , N ^4" -diphenyl- [1,1': 4 ', 1 '' -terphenyl] -4,4 '' - diamine (41)

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.55
• DSC: Melting point: 242 ° C (onset), sublimed material Glass transition temperature Tg: 102 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.34 (s, 6H, Me), 7.07 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph ), 7.16 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene unit of terphenylcore), 7.18 (s, 2H, CH terphenyl middle ring), 7.19 ("d" with fine splitting, J = 7.5 Hz, 4H, o-Ph), 7.28 ("d" with fine splitting, J = 8.5Hz, 4H, phenylene unit of terphenylcore), 7.31 ("t" with fine splitting, J = 7.5Hz, 4H, m-Ph), 7.33 ("d ", J = 9.0 Hz, 2H, naphthyl), 7.35 (" ddd ", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.40 (" ddd ", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.48 ("d", J = 2.0 Hz, 2H, naphthyl H-1), 7.61 ("d", J = 8.5 Hz, 2H, naphthyl), 7.76 ("d", J = 8.5Hz, 2H, naphthyl), 7.77 ("d", J = 7.5Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.14 (q, Me), 120.51 (d), 123.42 (d), 123.89 (d, phenylene or o-Ph or m-Ph), 124.69 (d), 124.78 (d), 124.88 (d, phenylene or o-Ph or m-Ph), 126.58 (d), 127.12 (d), 127.80 (d), 129.14 (d), 129.64 (d, phenylene or o-Ph or m-Ph), 130.39 (d, phenylene or o-Ph or m-Ph), 132.15 (d), 132.93 (s), 134.80 (s), 136.49 (s), 140.42 (s), 145.79 (s, C _ar -N), 146.76 (s, C _ar -N), 148.07 (s, C _ar -N). The missing quart. Carbon signal is most likely superimposed by the signal at 130.39 ppm, based on its signal intensity.

Elemental analysis: About [%]: C 90.14 H 5.82 N 4.04 exp. [%]: C 90.55 H 5.91 N 4.05 Conductivity (10 mol%): 1.36E-04 S / cm (d1).

2.2.16 Characterization N ⁴ , N ^{4 ''} - Di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^{4 ''} - bis (2,4-dimethylphenyl) - [1,1 ' : 4 ', 1''- terphenyl] -4,4''- diamine (17)

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.36
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg; 116 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.07 (s, 6H, ortho-Me), 2.36 (s, 6H, para-Me), 7.06 ("d" with fine splitting, J = 9.0 Hz, 8H, phenylene), 7.07 (br s, 4H, xylyl ring), 7.13 (br s, 2H, xylyl ring), 7.29 ("tt", J = 7.5 Hz, 1.0 Hz , 2H, p-Ph), 7.41 ("t" with fine splitting, J = 7.5 Hz, 4H, m-Ph), 7.48 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.52 ("d With fine splitting, J = 8.5 Hz, 4H, phenylene), 7.57 ("dd", J = 8.0 Hz, 1.5 Hz, 4H, o-Ph), 7.63 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 18.44 (q, ortho-Me), 21.05 (q, para-Me), 121.74 (d, phenylene or o-Ph or m-Ph), 121.76 (d, phenylene or o-Ph or m-Ph), 126.72 (d, phenylene or o-Ph or m-Ph), 126.95 (d, xylyl or p-Ph), 126.99 (i.e. , Phenylene or o-Ph or m-Ph), 127.61 (d, phenylene or o-Ph or m-Ph), 127.52 (d, phenylene or o-Ph or m-Ph), 128.50 (d, xylyl or p-phenylene). Ph), 129.03 (d, phenylene or o-Ph or m-Ph), 129.76 (d, xylyl or p-Ph), 132.71 (d, xylyl or p-Ph), 133.59 (s), 134.15 (s), 136.67 (s), 136.76 (s), 139.14 (s), 140.93 (s), 142.57 (s, C _ar -N), 146.97 (s, C _ar -N). The missing quart. Carbon signal is most likely superimposed by the signal at 146.97 ppm, based on its signal intensity.

Elemental analysis: About [%]: C 90.12 H 6.26 N 3.62 exp. [%]: C 90.20 H 6.38 N 3.65 Conductivities (10 mol%) 4.68E-04 S / cm (d1); 7.02E-05 S / cm (d2); 9.73E-06 S / cm (d3).

2.2.17 Characterization of N ⁴ , N ^{4 "} -bis (2,4-dimethylphenyl) -N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4,1'' -terphenyl] -4,4 "-diamine (16)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.63
• TLC (silica gel, ethyl acetate / n-hexane = 1:10): R _f = 0.52
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 113 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.06 (see 6H, ortho-Me), 2.37 (s, 6H, para-Me), 7.07 ("d" with fine resolution, J = 8.0 Hz, 4H, phenylene), 7.08 (presumed s, 4H, xylyl-CH, naphthyl H-1), 7.14 (br.s, 2H, xylyl-CH), 7.27 (br. s, 2H , Xylyl-CH), 7.28 ("d", J = 9.0 Hz, 2H, naphthyl), 7.31 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7) , 7.37 ("ddd", J = 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H-6 or H-7), 7.53 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.56 ( "D", J = 8.0 Hz, 2H, naphthyl), 7.64 (s, 4H, terphenyl middle ring), 7.71 ("d", J = 8.5 Hz, 2H, naphthyl), 7.74 ("d", J = 8.0 Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 18.48 (q, ortho-Me), 21.06 (q, para-Me), 117.32 (d), 121.88 (d, Terphenyl), 122.90 (d), 124.23 (d), 126.55 (d), 126.93 (d), 127.00 (d, terphenyl), 127.63 (d, terphenyl), 127.75 (d), 128.48 (d), 128.90 (i.e. ), 129.73 (d), 129.75 (5), 132.74 (d), 133.71 (s), 134.83 (s), 136.56 (s), 136.62 (s), 139.15 (s), 142.79 (s), 145.32 (s , C _ar -N), 147.21 (s, C _ar -N).

Elemental analysis: About [%]: C 89.96 H 6.15 N 3.89 exp. [%]: C 90.27 H 6.32 N 3.98 Conductivities (10 mol.%): 6.16E-04 S / cm (d1); 8.55E-05 S / cm (d2); 2.59E-05 S / cm (d3).

2.2.18 Characterization of N ⁴ , N ^{4 "} -bis (4-isopropylphenyl) -N ⁴ , N ^4" -di (naphthalen-2-yl) - [1,1 ': 4', 1 '' - terphenyl] -4,4 "-diamine (10)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.65
• DSC: Melting point: 258 ° C (onset), sublimed material Glass transition temperature Tg: 110 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.26 (d, ³ J = 7.0 Hz, 12H, Me), 2.91 ("quint", ³ J = 7.0 Hz, 2H, C H Me ₂ ), 7.10 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.17 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.18 ("d" with Fine splitting, J = 9.0 Hz, 4H, phenylene), 7.30 ("dd", J = 9.0 Hz, 2.0 Hz, 2H, naphthyl), 7.34 ("ddd", 8.0 Hz, 7.0 Hz, 1.0 Hz, 2H, naphthyl H -6 or H-7), 7.39 ("ddd", 8.0 Hz, 7.0 Hz, 1.5 Hz, 2H, naphthyl H-6 or H-7), 7.44 ("d", J = 2.0 Hz, 2H, naphthyl H -1), 7.55 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.60 ("d", J = 8.0 Hz, 2H, naphthyl), 7.66 (s, 4H, terphenyl middle ring), 7.74 ("D", J = 9.0Hz, 2H, naphthyl), 7.76 ("d", J = 8.0Hz, 2H, naphthyl).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 24.11 (q, Me), 33.88 (d, C HMe ₂ ), 120.09 (d, naphthyl), 124.04 (d, Phenylene), 124.54 (d, naphthyl), 124.67 (d, naphthyl), 125.35 (d, phenylene), 126.56 (d, naphthyl), 127.07 (d, naphthyl), 127.12 (d, phenylene), 127.67 (d, phenylene 127.76 (d, phenylene), 127.78 (d, naphthyl), 129.06 (d, naphthyl), 130.29 (s), 134.65 (s), 134.80 (s), 139.24 (s), 144.73 (s, C _ar -) N or C _Ar -iPr), 145.44 (s, C _ar -N or C _Ar -iPr), 145.82 (s, C _ar -N or C _Ar -iPr), 147.69 (s, C _ar -N or C _ar - Pr).

Elemental analysis: About [%]: C 89.80 H 6.46 N 3.74 exp. [%]: C 89.97 H 6.47 N 3.83 Conductivities (10 mol%): 1.16E-03 S / cm (d1); 3.23E-04 S / cm (d2); 6.20E-05 S / cm (d3).

2.2.20 Characterization of N ⁴ , N ^{4 ''} di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^{4 ''} -dimesityl- [1,1 ': 4', 1 '' -terphenyl] -4,4 "-diamine (20)

• TLC (silica gel, DCM / n-hexane = 1: 1): R _f = 0.57
• DSC: Melting point: no melting peak observed, sublimed material Glass transition temperature Tg: 141 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 2.05 (s, 12H, o-Me), 2.34 (s, 6H, p-Me), 7.00 (s, 4H , Mesityl-H), 7.07 ("dd", actually superimposed 2 × d, J = 8.5 Hz, 1.0 Hz, 8H, phenylene), 7.28 ("t" with fine splitting, J = 7.5 Hz, 2H, p-Ph) , 7.40 ("t", J = 7.5 Hz, 4H, m-Ph), 7.48 ("d" with fine splitting, J = 9.0 Hz, 4H, phenylene), 7.52 ("d" with fine splitting, J = 8.5 Hz, 4H, phenylene), 7.57 ("d" with fine splitting, J = 7.5Hz, 4H, o-Ph), 7.62 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 18.60 (q, o-Me), 21.11 (q, p-Me), 120.14 (d), 126.65 (d) , 126.88 (d, p-Ph), 126.92 (d), 127.65 (d), 127.87 (d), 129.04 (d), 130.27 (d), 133.15 (s), 133.67 (s), 137.50 (s), 137.92 (s), 139.09 (s), 140.11 (s), 140.96 (s), 145.57 (s, C _ar -N), 145.59 (s, C _ar -N). The missing quart. Carbon signal is most likely superimposed on the signal at 137.92 ppm, based on its significantly greater signal intensity compared to other quart. Carbons. Likewise, one of the phenylene CH signals is superimposed by other signals.

Elemental analysis: About [%]: C 89.96 H 6.54 N 3.50 exp. [%]: C 90.03 H 6.55 N 3.48 Conductivities (10 mol.%): 6.84E-04 S / cm (d1); 5.52E-05 S / cm (d2); 8.81E-06 S / cm (d3).

2.2.22 Characterization of N ⁴ , N ⁴ , N ^{4 ''} , N ^{4 ''} tetrakis (4- (tert-butyl) phenyl) - [1,1 ': 4', 1 '' - terphenyl] -4 , 4 '' - diamine (26)

• TLC (silica gel, DCM / n-hexane = 1: 2): R _f = 0.64
• DSC: Melting point: 336 ° C (peak), sublimed material Glass transition temperature Tg: 149 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H-NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.31 (s, 36H, CMe ₃ ), 7.04 ("d" with characteristic splitting, J = 8.5 Hz, 8H, C ₆ H ₄ 'Bu), 7.08 ("d" with characteristic fine splitting, J = 8.5 Hz, 4H, terphenyl), 7.30 ("d" with characteristic fine splitting, J = 8.5 Hz, 8H, C ₆ H ₄ ' Bu), 7.50 ("d" with characteristic splitting, J = 8.5 Hz, 4H, terphenyl), 7.62 (s, 4H, terphenyl middle ring).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] 31.48 (q, Me), 34.51 (s, C Me ₃ ), 123.11 (d, terphenyl), 124.46 (d, phenylene C ₆ H ₄ 'Bu), 126.44 (d, phenylene C ₆ H ₄ ' Bu), 127.03 (d, terphenyl), 127.58 (d, terphenyl), 133.89 (s, terphenyl), 139.21 (s, terphenyl), 145.29 (s, phenylene C ₆ H ₄ 'Bu), 146.36 (s, phenylene C ₆ H ₄ ' Bu), 147.93 (s, terphenyl C _Ar -N).

Elemental analysis: About [%]: C 88.28 H 8.17 N 3.55 exp. [%]: C 88.28 H 8.11 N 3.47 Conductivities (10 mol%): 1.67E-04 S / cm (d1); 8.92E-05 S / cm (d2); 3.46E-06 S / cm (d3). Connection (40)
Conductivities (10 mol%): 1.57E-04 S / cm (d1); 4.09E-05 S / cm (d2); 5.73E-07 S / cm (d3).

2.2.24 Characterization of N ⁴ , N ^{4 "} -di ([1,1'-biphenyl] -4-yl) -N ⁴ , N ^4" -bis (4- (tert-butyl) phenyl) -2 ', 5'-dimethyl- [1,1': 4 ', 1''- terphenyl] -4,4''- diamine (36)

• TLC (silica gel, DCM / n-hexane = 1: 3): R _f = 0.35
• DSC: Melting point: no melting point observed, sublimed material Glass transition temperature Tg: 131 ° C (onset), heating rate 10 K / min, sublimed material
• ¹ H NMR (CD ₂ Cl ₂ referenced to 5.31 ppm, 500.13 MHz): δ [ppm] = 1.34 (s, 18H, tBu), 2.33 (s, 6H, Me), 7.12 ("d" with characteristic splitting, J = 8.5 Hz, 4H, phenylene), 7.15 ("d" with characteristic splitting, J = 8.5 Hz, 4H, phenylene), 7.17 (s, 2H, terphenyl middle ring), 7.18 ("d" with more characteristic Fine splitting, J = 9.0 Hz, 4H, phenylene), 7.27 ("d" with characteristic fine splitting, J = 8.5 Hz, 4H, phenylene), 7.31 ("t" with detectable fine splitting, J = 7.5 Hz, 2H, p-Ph ), 7.35 ("d" with characteristic splitting, J = 8.5 Hz, 4H, phenylene), 7.42 ("t", J = 7.5 Hz, 4H, m-Ph), 7.51 ("d" with characteristic splitting, J = 8.5 Hz, 4H, phenylene), 7.59 ("d" with detectable fine splitting, J = 7.5 Hz, 4H, o-Ph).
• ¹³ C-NMR (CD ₂ Cl ₂ referenced to 53.73 ppm, 125.76 MHz): δ [ppm] = 20.16 (q, Me), 31.50 (q, t Bu), 34.56 (s, t Bu), 123.56 (d), 123.91 (d), 124.89 (d), 126.58 (d), 126.83 (d), 127.08 (d, p-Ph), 127.95 (d), 129.06 (d), 130.32 (d), 132.15 (d, CH) terphenyl middle ring), 132.92 (s), 135.08 (s), 136.16 (s), 140.46 (s), 140.93 (s), 145.13 (s, _Ar C-N or C _Ar t Bu), 146.79 (s, _Ar C - N or C _ar -tBu), 146.80 (s, C _ar -N or C _ar -tBu), 147.68 (s, C _ar -N or C _ar -tBu).

Elemental analysis: About [%]: C 89.68 H 7.06 N 3.27 exp. [%]: C 89.58 H 7.04 N 3.26 Conductivity (10 mol%): 5.71E-04 S / cm (d1)

Electronic component

Using the organic compounds according to the invention for producing doped organic semiconducting materials, which may be arranged in particular in the form of layers or electrical conduction paths, a multiplicity of electronic components or devices containing them can be produced. In particular doped semiconductor layers according to the invention for the preparation of organic diodes, in particular organic light emitting diodes (OLED), organic solar cells, especially those can be used with high rectification ratio such as 10 ³ -10 ^7, preferably 10 ^{4 to} 10 ^7, or 10 ⁵ -10. ⁷ The dopants according to the invention can be used to improve the conductivity of the doped layers and / or to improve the charge carrier injection of contacts into the doped layer. Particularly in the case of OLEDs, the component may have a pin structure or an inverted structure, without being limited thereto. However, the use of the doped semiconductor layers according to the invention is not limited to the above-mentioned advantageous embodiments. Also preferred are OLEDs that are ITO free. Furthermore, OLEDs are provided with at least one organic electrode. Preferred organic electrode (s) are conductive layers containing the following materials as main components: PEDOT-PSS, polyaniline, carbon nanotubes, graphite.

• 1. Träger, Substrat, z. B. Glas
• 2. Elektrode, löcherinjizierend (Anode = Pluspol), vorzugsweise transparent, z. B. Indium-Zinn-Oxid (ITO) oder FTO (Braz. J. Phys. V. 35 no. 4 pp. 1016–1019 (2005))
• 3. Löcherinjektionsschicht,
• 5. löcherseitige Blockschicht um Exzitonendiffusion aus der Emissionsschicht zu verhindern und Ladungsträger-Leckage aus der Emissionsschicht zu verhindern
• 6. lichtemittierende Schicht oder System von mehreren zur Lichtemission beitragenden Schichten, z. B. CBP (Carbazol-Derivate) mit Emitterbeimischung (z. B. phosphoreszenter Triplet Emitter Iridium-tris-phenylpyridin Ir(ppy)3) oder Alq3 (tris-quinolinatoaluminium) gemischt mit Emittermolekülen (z. B. fluoreszenter singulett Emitter Coumarin),
• 7. elektronenseitige Blockschicht um Exzitonendiffusion aus der Emissionsschicht zu verhindern und Ladungsträger-Leckage aus der Emissionsschicht zu verhindern, z. B. BCP (Bathocuproine),
• 8. Elektronentransportschicht (ETL), z. B. BPhen, Alq3 (tris-quinolinato-aluminium),
• 10. Elektrode, meist ein Metall mit niedriger Austrittsarbeit, elektroneninjizierend (Kathode = Minuspol), z. B. Aluminium.

The typical structure of a standard OLED can look like this:

• 1st carrier, substrate, z. Glass
• 2nd electrode, hole injecting (anode = positive pole), preferably transparent, z. Indium tin oxide (ITO) or FTO (Braz J. Phys., V. 35, no. 4 pp. 1016-1019 (2005)).
• 3. hole injection layer,
• 5. Holeside block layer to prevent exciton diffusion from the emission layer and prevent carrier leakage from the emission layer
• 6. Light-emitting layer or system of several contributing to the light emission layers, eg. B. CBP (carbazole derivatives) with emitter admixture (eg phosphorescent triplet emitter iridium-tris-phenylpyridine Ir (ppy) 3) or Alq3 (tris-quinolinatoaluminum) mixed with emitter molecules (eg fluorescence singlet emitter coumarin),
• 7. electron-side blocking layer to prevent exciton diffusion from the emission layer and to prevent charge carrier leakage from the emission layer, eg. B. BCP (Bathocuproine),
• 8. Electron Transport Layer (ETL), e.g. B. BPhen, Alq3 (tris-quinolinato-aluminum),
• 10. electrode, usually a metal with low work function, electron-injecting (cathode = negative pole), z. As aluminum.

Of course, layers can be omitted or a layer (or a material) can take on several properties, eg. For example, the layers 3-5, or the layers 7 and 8 can be combined. Other layers can also be used. Stacked OLEDs are also provided.

This design describes the non-inverted (anode on the substrate), substrate-emitting (bottom-emission) structure of an OLED. There are several concepts to describe substrate front emitting OLEDs (see references in DE 102 15 210.1 ), by all is meant that then the substrate-side electrode (in the non-inverted case, the anode) is reflective (or transparent to a transparent OLED) and the cover electrode is made (semi-) transparent. If the order of the layers is inverted (cathode on substrate) one speaks of inverted OLEDs (see references in DE 101 35 513.0 ). Here, too, performance losses can be expected without special measures.

A preferred design of the structure of an OLED according to the invention is the inverted structure (where the cathode is on the substrate) and wherein the light is emitted through the substrate. Furthermore, it is provided in one embodiment that the OLED is top emitting.

It is preferable that the hole injection layer directly adjoin the hole-side block layer with the hole injection layer being doped.

In another embodiment of the invention, it is preferred that the hole injection layer and the hole side block layer include the same matrix material.

In a particularly preferred embodiment of the invention, the hole-side block layer is at least 5 times, preferably at least 20 times thicker than the hole injection layer, wherein the hole-side block layer is undoped and the hole injection layer is doped.

OLEDs were made as follows:
A layer of compound (4) was doped with compound (d1). The doped layer was deposited on a ITO coated glass substrate by coevaporation of the structure (4) and dopant (d1) material under high vacuum. The concentration of the dopant in the matrix was 3.0 mol%, layer thickness 50 nm. Subsequently, a red emitter layer (20 nm) of compound (40) doped with iridium (III) bis (2-methyldibenzo [f, h] quinoxaline) (acetylacetonate) (076RE, from ADS), an undoped electron transport and hole block layer of 4- (naphthalen-1-yl) -2,7,9-triphenylpyrido [3,2-h] quinazoline (10 nm) , and subsequently a 4- (naphthalene) group doped with W (hpp) 4 (tetrakis (1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidinato) di (tungsten) (II)). 1-yl) -2,7,9-triphenylpyrido [3,2-h] quinazoline layer (50 nm, 10 mol%). Al (100 nm) was used as the cathode. Subsequently, the thus processed components were encapsulated against water with a lidded glass - a corresponding getter was previously introduced. Compound (40) was used as emitter matrix to compare only the variation of the transport layer. Nonetheless, the compounds of the invention can also be used as an emitter matrix.

The produced OLED has a voltage of 2.6 V at a current density of 10 mA / cm 2, with a quantum efficiency of 11%. The power at 10 mA / cm2 is 20.6 lm / W. A current density of 100 mA / cm2 can be achieved even at the low voltage of 3.0 V.

In a comparative experiment with an OLED prepared using relatively good compound (40) instead of (4), only 18.6 lm / W and a quantum efficiency of 9.9% can be achieved under the same measurement conditions. Similar comparison results are achieved with compound (3)).

• 1. Träger, Substrat, z. B. Glas
• 2. Anode, vorzugsweise transparent, z. B. Indium-Zinn-Oxid (ITO)
• 3. Löcherinjektionsschicht,
• 5. löcherseitige Zwischenschicht, bevorzugt Blockschicht um Exzitonendiffusion aus der Absorptionsschicht (optische aktive Schicht, auch Emissionsschicht genannt) zu verhindern und Ladungsträger-Leckage aus der Emissionsschicht zu verhindern,
• 6. Absorptionsschicht, typischerweise eine stark lichtabsorbierenden Schicht aus einen Heteroübergang (zwei oder mehrere Schichten oder Mischschicht) z. B. Mischschicht aus C60 und ZnPc,
• 7. Elektronentransportschicht,
• 10. Kathode, z. B. Aluminium.

The typical structure of an organic solar cell can look like this:

• 1st carrier, substrate, z. Glass
• 2. anode, preferably transparent, z. B. Indium Tin Oxide (ITO)
• 3. hole injection layer,
• 5. hole-side intermediate layer, preferably block layer in order to prevent exciton diffusion from the absorption layer (optical active layer, also called emission layer) and to prevent charge carrier leakage from the emission layer,
• 6. absorption layer, typically a highly light-absorbing layer of a heterojunction (two or more layers or mixed layer) z. B. mixed layer of C60 and ZnPc,
• 7. electron transport layer,
• 10. cathode, z. As aluminum.

Of course, layers can be omitted or a layer can take on several properties. Other layers can be used. Stacked (tandem) solar cells are provided. Variants such as transparent solar cells, inverted structure or m-i-p solar cells are also possible.

A preferred configuration of the structure of a solar cell is the inverted structure (with the cathode on the substrate) and where the light is incident through the substrate.

Another preferred configuration of the structure of a solar cell is the inverted structure (where the cathode is on the substrate) and where the light is incident through the anode.

Organic solar cells, also known as photovoltaic elements, were prepared as follows:
A layer of fullerene C60 was doped with W (hpp) 4. The doped layer was deposited by high vacuum mixing evaporation on a glass substrate coated with ITO. The concentration of the dopant in the matrix was 10 mol.%, Layer thickness 10 nm. Subsequently, an interruption of the vacuum an undoped 20 nm thickness 60 layer was prepared, followed by a mixing ratio, molar 1: 1, between C60 and ZnPc with a layer thickness of 30 nm. A 45 nm thick layer of compound (25) doped with 3 mol% followed by (d1). 2 nm (d1) was used as the injection, this improves the contact with the silver electrode, the other electrodes, such. B. Au this layer can be omitted. Ag (100 nm) was used as the anode. Subsequently, the thus processed components were encapsulated against water with a lidded glass a corresponding getter was previously introduced.

Under standard AM1.5 illumination, the following parameters were measured, Voc = 0.50 V, Jsc = 9.5 mA / cm ² , FF = 53%, and overall efficiency of 2.5%.

The same construction was repeated with compound (20) instead of compound (25) with very similar results.

Typically, the organic layer arrangement of an OLED or a solar cell comprises a plurality of organic layers arranged one above the other. Within the organic layer arrangement, one or more pn junctions may also be provided, as is known for stacked OLEDs (cf. EP 1 478 025 A2 In one embodiment, such a pn junction is formed by a p-doped hole transport layer and an n-doped electron transport layer formed in direct contact with each other. Such a pn junction is an electric charge generating structure in which When an electrical potential is applied, electrical charges are generated, preferably in the boundary region between the two layers.

In solar cells, the pn junction is also used to connect stacked heterojunctions and thus to add the voltage that this component generates ( US2006027834A ). The transitions have a similar function as tunnel junctions in stacked inorganic heterojunction solar cells, although the physical mechanisms are probably not the same.

The transitions are also used to get improved charge injection (extraction on solar cells) to the electrodes ( EP1808910 ).

To improve the electronic properties in an organic electronic device was in the document WO 2005/109542 A1 proposed to form a pn junction with a layer of an n-type organic semiconductor material and a layer of a p-type organic material, wherein the n-type organic semiconductor material layer contacts an electrode formed as an anode is. In this way, an improved injection of charge carriers in the form of holes is achieved in the layer of the p-type organic semiconductor material.

To stabilize the pn junction, a layer of another material is used as the intermediate layer. Such stabilized pn junctions are e.g. In US2006040132A described there is a metal used as an intermediate layer. OLEDs with this metal layer have a shorter life because of the diffusion of the metal atoms.

With the materials of the present invention, stable p-doped layers can be prepared which are provided in the pn junctions to produce stable organic semiconductor devices.

Further embodiments for solar cells can be made US7675057 B2 be removed.

The features disclosed in the specification and in the claims may be essential both individually and in any combination for realizing the invention in its various embodiments.

Claims (15)

Compound of the formula (I)

wherein R ^{1 is} selected from naphthyl or biphenylyl; R ^{2 is} selected from C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₅ -haloalkyl and C ₆ -C ₁₂ -aryloxy and R ² in the ortho and / or para position on the phenyl ring is present; R ^{3 is} selected from H or C ₁ -C ₅ alkyl; n = 1-3, it being preferred that like-named substituents are the same. Compound according to Claim 1, characterized in that R ^{2 is} C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy or C ₅ -C ₁₂ -aryloxy. A compound according to claim 1 or 2, characterized in that R ^{2 is} C ₁ -C ₅ alkyl, or phenoxy. Compound according to one of claims 1 to 3, characterized in that R ^{1 is} β-naphthyl. Compound according to one of claims 1 to 3, characterized in that R ^{1 is} 1,1'-biphenyl-4-yl. Compound according to one of the preceding claims, characterized in that R ^{3 is} H or methyl. Compound according to one of the preceding claims, characterized in that it is chosen from the compounds of the formula (III)

wherein R ⁴ and R ^{5 are} independently selected from H and R ² and not all R ⁴ and R ⁵ are H simultaneously. Compound according to one of the preceding claims, characterized in that R ^{2 is} methyl, iso-propyl or tert-butyl. Compound according to one of claims 1 to 3, characterized in that it is selected from

Compound according to claim 9, characterized in that it is selected from the formulas (4), (6), (10), (20), (25), (34), (36), (37). An organic semiconductive device comprising at least one layer containing a compound according to any one of the preceding claims. Organic semiconducting component according to claim 11, characterized in that the layer containing the compound according to one of claims 1 to 5 is doped. Organic semiconducting device according to claim 11, characterized in that the layer containing the compound according to one of claims 1 to 10 has at least one doped region, and at least one region which is less doped than the doped region or undoped. Organic semiconductive component according to one of claims 11 to 13, characterized in that the layer containing the compound is a hole transport layer or emitter layer. Organic semiconducting component according to one of Claims 11 to 14, characterized in that it is an organic light-emitting diode (OLED) or a photovoltaic component, preferably a solar cell.