WO2019114765A1 - Bipolar compound, high polymer, mixture, composition, organic electronic component, and applications - Google Patents

Abstract

The present invention relates to a bipolar compound, a high polymer, mixture, and composition comprising same, and applications thereof. In the bipolar compound, by respectively connecting a hole transport unit and an electron transport unit to a phenyl containing an ortho-group substitution, the resonance factor of the bipolar compound is effectively increased and, at the same time, the molecular spatial structure is further regulated, thus favoring increased component performance and stability of the compound, and providing a feasible solution for increasing the performance and service life of an organic electronic component.

Description

Bipolar compounds, polymers, mixtures, compositions, organic electronic devices and applications

This application claims priority on Chinese patent application filed on December 14, 2017, the Chinese Patent Office, Application No. 201711341843.8, entitled "A Class of Bipolar Compounds, Mixtures, Compositions and Their Applications in Organic Electronic Devices" The entire contents are hereby incorporated by reference.

Technical field

This invention relates to bipolar compounds, including polymers, mixtures and compositions thereof, organic electronic devices and applications. The invention further relates to an electronic device comprising the bipolar compound and to its use, in particular in an electroluminescent device.

Background technique

Organic semiconductor materials have many advantages such as various structures, relatively low manufacturing cost, and superior photoelectric performance, and have great potential in applications such as organic light-emitting diodes (OLEDs) such as flat panel displays and illumination.

In order to improve the luminescence performance of organic light-emitting diodes and promote the industrialization process of organic light-emitting diodes, various organic photoelectric performance material systems have been widely developed. However, the performance of OLEDs, especially performance and lifetime, still needs to be further improved. Efficient and stable organic optoelectronic performance materials are urgently needed to be developed.

In terms of the host material, the host material plays an important role in energy transfer and exciton dispersion in the light-emitting layer. From the aspect of energy transmission, the host material needs to have suitable HOMO and LUMO energy levels, which can reduce the potential barrier of electron and hole injection; the triplet energy level of the host material is higher than the triplet energy level of the light-emitting guest material, which can prevent The rotation of energy; the host material needs to have a certain charge transfer balance ability, so that the exciton recombination region is concentrated in the center of the luminescent layer to achieve high energy utilization efficiency and device stability. Considering the exciton dispersion, the structure of the host material has suitable sterically hindered structural units, which can effectively prevent dense packing between molecules and act as excitons to reduce the aggregation quenching of triplet excitons.

In the prior art, a bipolar compound is often used as a host material. For example, a technique discloses that a compound formed by using a hole transport unit and an electron transport unit as a host material can simultaneously transport holes and electrons, and can obtain good results. Device performance. However, the device performance and lifetime of such host materials still need to be further improved. The new material system needs further development.

Summary of the invention

In view of the above deficiencies of the prior art, it is an object of the present invention to provide a bipolar compound, including the high polymer, the mixture and the composition thereof, and the use thereof, aiming at solving the low performance and low life of the existing organic electronic device. The problem.

The technical solution of the present invention is as follows:

A bipolar compound, as shown in the general formula (1):

among them,

X independently represents a single bond, N(R ¹ ), C(R ¹ R ² ), Si(R ¹ R ² ), O, C=N(R ¹ ), C=C(R ¹ R ² ), P (R ¹ ), P(=O)R ¹ , S, S=O or SO ₂ ; wherein each occurrence of R ¹ and R ² independently represents H, D, substituted or unsubstituted carbon atoms 1 An alkyl group of ～30, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 60 ring atoms or an aromatic heterocyclic group;

L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aromatic group having 5 to 60 ring atoms. a hydrocarbon group or an aromatic heterocyclic group;

Z ¹ , Z ² , and Z ³ each independently represent N or CH, and at least one of Z ¹ , Z ² , and Z ³ is an N atom;

Ar ¹ and Ar ² are each independently represented as a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 30 ring atoms, wherein at least one ring atom number of Ar ¹ and Ar ² is more than 6;

Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 60 ring atoms.

The above bipolar compounds, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L, may each independently comprise one or more combinations of the following structural groups:

among them,

X ¹ -X ¹² respectively represent CR ³ or N, and X ¹ -X ^{6 are} not N at the same time;

Y is selected from N(R ⁴ ), C(R ⁴ R ⁵ ), Si(R ⁴ R ⁵ ), C(=O), S or O;

R ³ represents H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, substituted or unsubstituted alkyl having 1 to 30 carbon atoms a substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom number of 5 to 60 aromatic hydrocarbon groups or an aromatic heterocyclic group; and R ⁴ and R ⁵ have the same meanings as R ¹ .

Preferably, the above bipolar compound, wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L may each independently comprise one of the following chemical formulas, wherein H on the ring may be optionally substituted:

The above bipolar compound comprises a structure represented by any of the formulae (2) to (6):

Among them, X, L, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ^{5 have} the same meanings as described above.

The above bipolar compound is preferably one of the following structural formulas:

The above bipolar compound is characterized in that the bipolar compound has T ₁ ≥ 2.2 eV, preferably ≥ 2.3 eV, more preferably ≥ 2.4 eV, and most preferably ≥ 2.5 eV. T1 represents the triplet level of the bipolar compound.

A high polymer comprising at least one repeating unit comprising a structural unit represented by the chemical formula (1).

A mixture comprising a bipolar compound or polymer as described above, and at least one organic functional material, said organic functional material being selected from at least one of the following materials: a hole injecting material ( HIM), hole transport material (HTM), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), illuminator (Emitter), host material (Host) ) and organic dyes.

A composition comprising a bipolar compound or polymer as described above, and at least one organic solvent.

A use of a bipolar compound or polymer as described above in an organic electronic device.

An organic electronic device comprising a functional layer comprising a bipolar compound or polymer as described above.

The above organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic sensor, and an organic plasma. Organic Plasmon Emitting Diode.

Preferably, the organic electronic device is an electroluminescent device, and the functional layer of the electroluminescent device comprises a light-emitting layer and an electron transport layer, wherein the light-emitting layer comprises a bipolar compound or a polymer as described above, or a light-emitting layer A bipolar compound or polymer and a phosphorescent emitter as described above, or an electron transport layer comprising a bipolar compound or polymer as described above.

Advantageous Effects: The bipolar compound according to the present invention is used in an OLED, particularly as a light-emitting layer material, to provide high luminescent properties and device lifetime. The possible reasons are as follows, but are not limited thereto. The two segments of the phenyl group substituted with an ortho-aryl group are respectively connected to the hole transporting unit and the electron transporting unit, and on the one hand, the spatial structure of the compound can be adjusted. On the other hand, it can significantly improve the resonance factor of the compound, can effectively prevent dense packing between molecules and reduce the concentration of excitons, and can achieve more efficient energy transfer. Thereby effectively improving the luminescent properties and lifetime of the associated organic light emitting diode.

Detailed ways

The present invention provides a class of bipolar compounds, including mixtures and compositions thereof, and uses thereof. In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the host material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.

In the present invention, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

In the present invention, "substituted" in the expression "substituted or unsubstituted" means that the hydrogen atom in the substituent is substituted by a substituent, and "unsubstituted" means that the hydrogen atom on the group is unsubstituted. Replaced. Wherein the substituent may be selected from the group consisting of D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, boron-containing, silicon-containing The group and the alkyl group having 1 to 50 (preferably 1 to 18, more preferably 1 to 8) carbon atoms and 3 to 50 ring atoms (preferably 3 to 10, more preferably 3) Further, ～8 is more preferably a cycloalkyl group of 5 or 6) or an aromatic hydrocarbon group or an aromatic heterocyclic group having 3 to 50 (preferably 3 to 25, more preferably 3 to 18) ring atoms.

In the present invention, the "number of ring atoms" means a structural compound (for example, a monocyclic compound, a fused ring compound, a crosslinking compound, a carbocyclic compound, or a heterocyclic compound) obtained by synthesizing a ring bond, which constitutes the ring itself. The number of atoms in an atom. When the ring is substituted by a substituent, the atom contained in the substituent is not included in the ring-forming atom. The "number of ring atoms" described below is also the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the present invention, "aromatic hydrocarbon group" or "aromatic group" means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system. "Aromatic heterocyclic group" or "heteroaromatic group" refers to a hydrocarbon group (containing a hetero atom) comprising at least one aromatic heterocyclic ring, including a monocyclic group and a polycyclic ring system. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or aromatic. For the purposes of the present invention, an aromatic or aromatic heterocyclic ring system includes not only a system of an aryl or a aryl group, but also a plurality of aryl or aryl groups may also be interrupted by short non-aromatic units (<10%). Non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.

Specifically, examples of the aromatic hydrocarbon group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, examples of the aromatic heterocyclic group are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazepine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

The present invention provides a bipolar compound represented by the formula (1),

among them,

X independently represents a single bond, N(R ¹ ), C(R ¹ R ² ), Si(R ¹ R ² ), O, C=N(R ¹ ), C=C(R ¹ R ² ), P (R ¹ ), P(=O)R ¹ , S, S=O or SO ₂ ; wherein each occurrence of R ¹ and R ² independently represents H, D, substituted or unsubstituted carbon atoms 1 An alkyl group of ～30, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 60 ring atoms or an aromatic heterocyclic group;

L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aromatic group having 5 to 60 ring atoms. a hydrocarbon group or an aromatic heterocyclic group;

Z ^1, Z ^2, Z ³ each independently represent N or CH, and Z ^1, Z ^2, Z ³ Species at least one N atom;

Ar ¹ and Ar ² are each independently represented as a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 30 ring atoms, wherein at least one ring atom number of Ar ¹ and Ar ² is more than 6;

Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 60 ring atoms.

In some preferred embodiments, X represented by the formula (1) is a single bond, N(R ¹ ), C(R ¹ R ² ), O or S; in a more preferred embodiment, X is Single button, O or S.

In some preferred embodiments, R ¹ and R ² represented by the formula (1) are each independently represented by a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom number of 3 ～20 cycloalkyl, substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 40 ring atoms; and in a more preferred embodiment, R ¹ and R ² are independently represented as substituted or not a substituted alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or an aromatic heterocyclic group In a most preferred embodiment, R ¹ and R ² are each independently represented by a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a substitution. Or an unsubstituted aromatic hydrocarbon group having 5 to 20 ring atoms or an aromatic heterocyclic group.

In some preferred embodiments, L represented by the formula (1) is represented by a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom number of 3 to 20 a cycloalkyl group, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 ring atoms or an aromatic heterocyclic group; in a more preferred embodiment, L is represented by a single bond, a substituted or unsubstituted carbon atom number of 1 ～15 alkyl, substituted or unsubstituted cycloalkyl having 3 to 15 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or aromatic heterocyclic group; most preferred embodiment In the examples, L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted ring atom number of 5 ～20 aromatic hydrocarbon group or aromatic heterocyclic group.

In some preferred embodiments, at least two of Z ¹ , Z ² , and Z ³ represented by the formula (1) are N atoms, such as the following formulas (4) to (6); more preferred embodiments In the examples, Z ¹ , Z ² and Z ^{3 are} all N atoms, as in the following general formula (6).

In some preferred embodiments, Ar ¹ and Ar ² represented by the formula (1) are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 25 ring atoms; In a more preferred embodiment, Ar ¹ and Ar ² are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 20 ring atoms; in a most preferred embodiment, Ar ¹ , Ar ^{2 is} independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 15 ring atoms, wherein at least one ring atom number of Ar ¹ and Ar ² is more than 6; more preferred examples In the above, both Ar ¹ and Ar ² have more than 6 ring atoms.

In some preferred embodiments, Ar ³ , Ar ⁴ , and Ar ⁵ represented by the formula (1) are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic ring having 5 to 40 ring atoms. In a more preferred embodiment, Ar ³ , Ar ⁴ and Ar ⁵ are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 30 ring atoms; the most preferred embodiment In the examples, Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 20 ring atoms.

In some preferred embodiments, the above bipolar compound, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L, may each independently comprise one or more combinations of the following structural groups:

among them,

X ¹ -X ¹² respectively represent CR ³ or N, and X ¹ -X ^{6 are} not N at the same time;

Y is selected from N(R ⁴ ), C(R ⁴ R ⁵ ), Si(R ⁴ R ⁵ ), C(=O), S or O;

R ³ represents H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, substituted or unsubstituted alkyl having 1 to 30 carbon atoms a substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom number of 5 to 60 aromatic hydrocarbon groups or an aromatic heterocyclic group; and R ⁴ and R ⁵ have the same meanings as R ¹ .

In some more preferred embodiments, the above bipolar compound, wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L may each independently comprise one of the following chemical formulas, wherein H can be arbitrarily replaced:

In some most preferred embodiments, the above bipolar compound, wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L may each independently comprise one of the following chemical formulas, wherein H can be arbitrarily replaced:

In certain preferred embodiments, the bipolar compound comprises a structure represented by any of the formulae (2)-(6):

Here, the meanings of X, L, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are as described above.

The compounds represented by the formula (1) are exemplified below, but are not limited thereto:

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy levels T ₁ , LUMO, HOMO, and the resonance factor f (S1) play a key role. The following is an introduction to the determination of these energy levels.

The LUMO and HOMO levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet level T _{1 of the} organic material can be measured by low temperature time-resolved luminescence spectroscopy or by quantum simulation calculations (eg by Time-dependent DFT), such as by the commercial software Gaussian 09W (Gaussian Inc.), a specific simulation method. See WO2011141110 or as described below in the examples.

It should be noted that the absolute values of LUMO, HOMO, T ₁ depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different LUMO/ HOMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, T ₁ , and f(S1) are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

Preferably, the above bipolar compound has a resonance factor f(S1) ≥ 0.001, preferably f(S1) ≥ 0.005, more preferably f(S1) ≥ 0.04, and most preferably f(S1) ≥ 0.08.

The bipolar compound according to the present invention can be used as a functional material in an electronic device. Functional materials can be classified into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injecting materials (EIM), electron blocking materials (EBM), and hole blocking materials (HBM). Emitter, host material. In a preferred embodiment, the bipolar compound according to the invention may be used as a host material, or an electron transport material, or a hole transport material. In a more preferred embodiment, the bipolar compound according to the invention can be used as a phosphorescent host material.

As a phosphorescent host material, there must be an appropriate triplet level, T1. In certain embodiments, according to the bipolar compound of the invention, T1 ≥ 2.3 eV, preferably ≥ 2.4 eV, more preferably ≥ 2.5 eV, still more preferably ≥ 2.6 eV, and most preferably ≥ 2.7 eV.

In a more preferred embodiment, the above bipolar compound has ((LUMO+1)-LUMO) ≥ 0.1 eV, preferably ≥ 0.15 eV, more preferably ≥ 0.20 eV, still more preferably ≥ 0.25. eV is preferably ≥0.30 eV.

In another preferred embodiment, the above bipolar compound (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, more preferably ≥ 0.35 eV, preferably ≥ 0.40 eV.

In a preferred embodiment, the compounds according to the present invention, the bipolar, the glass transition temperature T _g ≥100 ℃, in a preferred embodiment, its T _g ≥120 ℃, in a more preferred embodiment its T _g ≥140 ℃, in a more preferred embodiment, its T _g ≥160 ℃, in a most preferred embodiment, its T _g ≥180 ℃.

In a more preferred embodiment, according to the bipolar compound of the present invention, the hydrogen atom may be partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, Fortunately, 30% of H is destroyed, and preferably 40% of H is deuterated.

In a preferred embodiment, the bipolar compound according to the invention is a small molecule material.

In a preferred embodiment, the bipolar compound according to the invention is used in an evaporated OLED device. For this purpose, the compounds according to the invention have a molecular weight of ≤1000 g/mol, preferably ≤900 g/mol, very preferably ≤850 g/mol, more preferably ≤800 g/mol, most preferably ≤700 g/mol.

In certain embodiments, the bipolar compound according to the present invention has luminescent properties with an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm, more More preferably it is between 400 and 600 nm, preferably between 400 and 500 nm. The luminescence referred to herein means photoluminescence or electroluminescence.

In certain preferred embodiments, the bipolar compound according to the present invention has a photo or electroluminescence efficiency of ≥ 30%, preferably ≥ 40%, more preferably ≥ 50%, and most preferably ≥ 60%. .

The present invention also relates to a high polymer in which at least one repeating unit contains the structure represented by the general formula (1). In certain embodiments, the high polymer is a non-conjugated high polymer wherein the structural unit as shown in the general formula (1) is on the side chain. In another preferred embodiment, the high polymer is a conjugated high polymer.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤ 3000 g/mol, preferably ≤ 2000 g/mol, preferably ≤ 1500 g/mol.

The polymer, that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Further, in the present invention, the high polymer also includes a dendrimer. For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

The conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp2 hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene), the main chain thereof. The C atom on it can also be replaced by other non-C atoms, and when the sp2 hybrid on the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer. Further, in the present invention, the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

In a preferred embodiment, the method for synthesizing the high polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the polymer according to the invention has a glass transition temperature (Tg) ≥ 100 ° C, preferably ≥ 120 ° C, more preferably ≥ 140 ° C, more preferably ≥ 160 ° C, optimal. It is ≥180 °C.

In a preferred embodiment, the polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably 1 ～2 is most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 40. More preferably, it is 150,000 to 300,000, and most preferably 200,000 to 250,000.

The invention further relates to a mixture comprising, for example, one of the above bipolar compounds or polymers, and at least one other organic functional material. The other organic functional material includes hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM), electron Barrier material (EBM), organic host material (Host), singlet illuminant (fluorescent illuminant), organic thermal excitation delayed fluorescent material (TADF material), triplet illuminant (phosphorescent illuminant), especially luminescent organic metal Complexes, and organic dyes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated by reference. The organic functional material may be a small molecule and a high polymer material.

In a preferred embodiment, the mixture comprises a bipolar compound or polymer according to the invention, and a phosphorescent emitter. Here, the bipolar compound according to the present invention may be used as a host, and the phosphorescent illuminant is ≤ 30% by weight, preferably ≤ 25% by weight, more preferably ≤ 20% by weight.

In another preferred embodiment, the mixture comprises a bipolar compound or polymer according to the invention, another host material and a phosphorescent emitter. The bipolar compound according to the invention herein as a co-host material has a weight percentage of ≥ 10% by weight, preferably ≥ 20% by weight, more preferably ≥ 30% by weight, most preferably ≥ 40% by weight.

In a more preferred embodiment, the mixture comprises a bipolar compound or polymer according to the invention, a phosphorescent emitter and a host material. In such an embodiment, the bipolar compound according to the invention may be used as an auxiliary luminescent material in a weight ratio to phosphorescent emitter of from 1:2 to 2:1. In another preferred embodiment, the organic compound according to the present invention a T ₁ higher than the phosphorescent emitter.

In certain embodiments, the mixture comprises a bipolar compound or polymer according to the invention, and another TADF material.

In other preferred embodiments, the mixture comprises a bipolar compound or polymer according to the invention, and another ETM material.

The subject material, phosphorescent material and TADF material are described in some detail below (but are not limited thereto). 1. Triplet Host Material (Triplet Host):

The example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy level is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant. Examples of metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer The value is from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-tooth ligand in which a metal is coordinated to an O and N atom. m is an integer whose value ranges from 1 to the maximum coordination number of the metal;

In one embodiment, M is optional for Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazine, anthraquinone, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, Quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopypyridine, benzothienopyridine, thienopyridine, benzoselenophene Pyridine and selenophene benzopyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or Hong heterocyclic group, and at least one of the following groups coupled together directly or through another, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein, each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.

In a preferred embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

. R ² -R ⁷ have the same meaning as R ¹ , X ^{9 is} selected from CR ¹ R ² or NR ¹ , and Y is selected from CR ¹ R ² or NR ¹ or O or S. R ¹ , n,, X ¹ -X ⁸ , and Ar ¹ to Ar ³ have the same meanings as described above.

Examples of suitable triplet host materials are listed in the table below but are not limited to this:

2. Phosphorescent materials

Phosphorescent emitters are also referred to as triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In a preferred embodiment, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.

Preferentially, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene. A quinolinol derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;

Ar1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Ar2 may be the same or different at each occurrence, and is a cyclic group containing at least one C atom through which a cyclic group is bonded to a metal; Ar1 and Ar2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group; each occurrence of L' may be the same or different and is a bidentate chelate auxiliary ligand, preferably a monoanion pair Teeth chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005 /0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219A1, US 20090061681A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998 , 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462A1, WO 2007095118A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1, WO 2013094620A1, W O 2013174471 A1, WO 2014031977 A1, WO 2014112450 A1, WO 2014007565 A1, WO 2014038456 A1, WO 2014024131 A1, WO 2014008982 A1, WO 2014023377 A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the table below:

3.TADF material

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE _st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, and secondly ΔEst < 0.2 eV, preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al. Chem. Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. .Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. Al.J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby incorporated by reference to The entire contents are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below:

Another object of the invention is to provide a material solution for printing OLEDs.

For this purpose, the bipolar compounds according to the invention have a molecular weight of ≥ 700 g/mol, preferably ≥ 900 g/mol, very preferably ≥ 900 g/mol, more preferably ≥ 1000 g/mol, most preferably ≥ 1100 g/mol.

In other preferred embodiments, the bipolar compound or polymer according to the invention has a solubility in toluene of > 10 mg/ml, preferably > 15 mg/ml, most preferably > 20 mg/ml at 25 °C.

The invention still further relates to a composition or ink comprising a bipolar compound or polymer according to the invention and at least one organic solvent.

The viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.

In a preferred embodiment, the ink according to the invention has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; In the range of 25dyne/cm to 33dyne/cm.

In another preferred embodiment, the ink according to the present invention has a viscosity at an operating temperature or 25 ° C in the range of about 1 cps to 100 cps; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps; It is in the range of 4.0cps to 20cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink. The ink containing the metal organic complex or polymer according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used. Generally, the composition according to the present invention comprises a functional material (i.e., a bipolar compound or a high polymer) in a weight ratio of from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably. It is in the range of 0.5% to 15% by weight, more preferably in the range of 0.5% to 10% by weight, most preferably in the range of 1% to 5% by weight.

In some embodiments, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention. Solvent, or aromatic ether solvent.

Examples of solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, two Hexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene , diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropane Pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetrahydronaphthalene Ketone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methyl Acetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2 - anthrone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene, butyl Oxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl) Benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenethyl ether, 1,2,4-trimethoxybenzene, 4 -(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans -p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl Ether, pentanyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; Ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, oleic acid Alkyl esters and the like.

Further, according to the ink of the present invention, the at least one solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, Toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1 , 1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The composition in the examples of the present invention may comprise from 0.01 to 20% by weight of the bipolar compound according to the invention or a mixture thereof, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably 0.25 to 5 wt% of a bipolar compound or a mixture thereof.

The invention further relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particularly preferably by a printing or coating process.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are inkjet printing, jet printing and gravure printing. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

The preparation method as described above, characterized in that the formed functional layer has a thickness of from 5 nm to 1000 nm.

The invention further relates to the use of a bipolar compound or polymer according to any of the preceding claims in an organic electronic device.

The invention further relates to an organic electronic device comprising a functional layer comprising a bipolar compound or polymer as described above.

The organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.

In certain particularly preferred embodiments, the organic electroluminescent device comprises at least one luminescent layer comprising a bipolar compound or polymer as described above.

The organic electroluminescent device comprises a substrate, an anode, at least one luminescent layer, a cathode, and optionally a hole transport layer or an electron transport layer. In certain embodiments, a compound or polymer according to the invention is included in the hole transport layer. In a preferred embodiment, a compound or polymer according to the invention is included in the luminescent layer, more preferably a compound or polymer according to the invention is included in the luminescent layer, And at least one luminescent material, which may be preferably a fluorescent illuminant, a phosphorescent illuminant, or a TADF material.

The device structure of the electroluminescent device will be described below, but is not limited thereto.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. (HBL). Materials suitable for use in these functional layers are described in detail above.

In another preferred embodiment, in the light-emitting device according to the invention, an electron transport layer (ETL) or a hole blocking layer (HBL) comprises an organic compound or polymer according to the invention, and a method of processing by solution Prepared.

The light-emitting device according to the present invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Specific embodiment

1. A method of synthesizing a compound according to the present invention is exemplified, but the present invention is not limited to the following examples.

(1) Synthesis of Compound (2-2):

(17.4 g, 80 mmol) of compound 2-2-1, (20.1 g, 80 mmol) of compound 2-2-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization, yield 90%.

Under nitrogen atmosphere, (17.9 g, 40 mmol) of compound 2-2-3 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, 45 mmol of n-butyllithium was slowly added dropwise, and the reaction was carried out for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to yield 85%.

(9.9 g, 20 mmol) of compound 2-2-4 and (5.3 g, 20 mmol) of compound 2-2-5, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography, yield 70%.

(2) Synthesis of compound (4-12):

(22.6 g, 80 mmol) of compound 4-12-1, (20.1 g, 80 mmol) of compound 2-2-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization to yield 85%.

Under a nitrogen atmosphere, (20.6 g, 40 mmol) of compound 4-12-2 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, and 45 mmol of n-butyllithium was slowly added dropwise for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to give a yield of 80%.

(10.3 g, 20 mmol) of compound 4-12-3 and (5.3 g, 20 mmol) of compound 4-12-4, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography to yield 65% yield.

(3) Synthesis of compound (5-8):

Compound (2-6-1, (20. The base formamide is added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, and most of the solvent is rotated, and the reaction liquid is inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization to yield 85%.

Under a nitrogen atmosphere, (22.6 g, 40 mmol) of compound 5-8-2 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, 45 mmol of n-butyllithium was slowly added dropwise, and the reaction was carried out for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to give a yield of 80%.

(12.2 g, 20 mmol) of compound 5-8-3 and (5.3 g, 20 mmol) of compound 5-8-4, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography, yield 70%.

(4) Synthesis of compound (6-16):

(21.4 g, 80 mmol) of compound 6-16-1, (20.1 g, 80 mmol) of compound 2-2-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization to yield 85%.

Under a nitrogen atmosphere, (19.9 g, 40 mmol) of compound 6-16-2 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, 45 mmol of n-butyllithium was slowly added dropwise, and the reaction was carried out for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to give a yield of 80%.

Under a nitrogen atmosphere, (10.9 g, 20 mmol) of compound 6-16-3 and (5.4 g, 20 mmol) of compound 6-16-4, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography to yield 65% yield.

(5) Synthesis of compound (6-21):

(21.4 g, 80 mmol) of compound 6-21-1, (20.1 g, 80 mmol) of compound 6-21-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization, yield 90%.

Under a nitrogen atmosphere, (19.9 g, 40 mmol) of compound 6-21-3 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, 45 mmol of n-butyllithium was slowly added dropwise, and the reaction was carried out for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to give a yield of 80%.

Under a nitrogen atmosphere, (10.9 g, 20 mmol) of compound 6-21-4 and (5.4 g, 20 mmol) of compound 6-16-4, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography to yield 65% yield.

(6) Synthesis of compound (6-35):

(66.6 g, 80 mmol) of compound 6-35-1, (24.1 g, 80 mmol) of compound 6-21-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization, yield 80%.

Under a nitrogen atmosphere, (24.6 g, 40 mmol) of compound 6-35-3 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, and 45 mmol of n-butyllithium was slowly added dropwise for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to yield 85%.

(13.2 g, 20 mmol) of compound 6-35-4 and (5.4 g, 20 mmol) of compound 6-16-4, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography to yield 65% yield.

(7) Synthesis of compound (6-37):

(17.4 g, 80 mmol) of compound 2-2-1, (20.1 g, 80 mmol) of compound 2-2-2, (39.1 g, 120 mmol) of cesium carbonate and 200 mL of N,N-dimethyl The base formamide was added to a 500 mL three-necked flask, and heated to 150 ° C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and most of the solvent was rotated, and the reaction liquid was inverted into 400 mL of purified water to precipitate a solid. The mixture was suction filtered, and the residue was collected and purified by recrystallization, yield 90%.

Under nitrogen atmosphere, (17.9 g, 40 mmol) of compound 6-37-1 and 150 mL of anhydrous tetrahydrofuran were added to a 250 mL three-necked flask, and the temperature was lowered to -78 ° C, 45 mmol of n-butyllithium was slowly added dropwise, and the reaction was carried out for 2 hours. Inject 50 mmol of isopropanol pinacol borate once, let the reaction rise to room temperature, continue the reaction for 12 hours, add pure water to quench the reaction, spin off most of the solvent, extract with dichloromethane and wash 3 times. The organic phase was collected, dried and recrystallized to yield 85%.

(9.9 g, 20 mmol) of compound 6-37-2 and (6.4 g, 20 mmol) of compound 6-37-3, (1.15 g, 1 mmol) of tetrakis(triphenylphosphine)palladium, (1.3) g, 4 mmol) tetrabutylammonium bromide, (1.6 g, 40 mmol) sodium hydroxide, (10 mL) water and (60 mL) toluene were added to a 150 mL three-necked flask, and the reaction was stirred at 80 ° C for 12 hours to complete the reaction. The liquid was evaporated to evaporate most of the solvent, washed with dichloromethane for 3 times, and the organic liquid was collected and purified by silica gel column chromatography to yield 65% yield.

Comparative Examples Ref-1 and Ref-2 (WO):

2. Energy structure of organic compounds

The energy level of the organic material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, use the semi-empirical method "Ground State/DFT/Default Spin/B3LYP" and the base group "6-31G(d)" (Charge 0/Spin Singlet) to optimize the molecular geometry. Then the energy structure of the organic molecule is determined by TD-DFT. The method (inclusive time density functional theory) calculates "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results are shown in Table 1, where ΔHOMO=HOMO-(HOMO-1), ΔLUMO=(LUMO+1)-LUMO:

Table I

3. Preparation and characterization of OLED devices

In the present embodiment, the compounds (6-16), (6-21), (6-35), (6-37), Ref-1 and Ref-2 were used as the host materials, respectively, as shown in the following figure Ir(mphq) ₂ acac as a luminescent material, HATCN as a hole injecting material, SFNFB as a hole transporting material, NaTzF ₂ as an electron transporting material, Liq as an electron injecting material, and a device structure of ITO/HATCN/SFNFB/host material: Emitter ( 3%)/NaTzF ₂ : Liq/Liq/Al electroluminescent device.

The above materials HATCN, SNFFB, Ir(mphq) ₂ acac, NaTzF ₂ , Liq are all commercially available, such as Jilin Elound (Jilin OLED Material Tech Co., Ltd, www.jl-oled.com), or The synthesis methods are all prior art, as described in the prior art, and will not be described herein.

The preparation process of the OLED device described above will be described in detail below through specific embodiments. The structure of the OLED device (such as Table 2) is: ITO/HATCN/SFNFB/body material: Emitter (3%)/NaTzF ₂ : Liq/Liq/ Al, the preparation steps are as follows:

a, ITO (indium tin oxide) conductive glass substrate cleaning: using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;

b, HATCN (30nm), SNFFB (50nm), host material: 3% Emitter (40nm), NaTzF ₂ : Liq (30nm), Liq (1nm), Al (100nm) in high vacuum (1 × 10 ^-6 mbar Medium heat evaporation;

c. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

Table 2

OLED device	Body material	T90@1000nits
OLED1	(6-16)	3.2
OLED2	(6-21)	4.2
OLED3	(6-35)	3.8
OLED4	(6-37)	3.5
RefOLED-1	Ref-1	1.5
RefOLED-2	Ref-2	1

The current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. It has been found that the luminescence lifetime of the bipolar compound having the ortho-substituent group of the present invention is relatively high in the same type of device, and is more than twice that of RefOELD. It can be seen that the lifetime of the OLED device prepared by using the organic compound of the invention is greatly improved.

Claims (12)

1. A bipolar compound as shown in the formula (1):

   

   among them,

   X independently represents a single bond, N(R ¹ ), C(R ¹ R ² ), Si(R ¹ R ² ), O, C=N(R ¹ ), C=C(R ¹ R ² ), P (R ¹ ), P(=O)R ¹ , S, S=O or SO ₂ ; wherein each occurrence of R ¹ and R ² independently represents H, D, substituted or unsubstituted carbon atoms 1 An alkyl group of ～30, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 60 ring atoms or an aromatic heterocyclic group;

   L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aromatic group having 5 to 60 ring atoms. a hydrocarbon group or an aromatic heterocyclic group;

   Z ¹ , Z ² , and Z ³ each independently represent N or CH, and at least one of Z ¹ , Z ² , and Z ³ is an N atom;

   Ar ¹ and Ar ² are each independently represented as a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 30 ring atoms, wherein at least one ring atom number of Ar ¹ and Ar ² is more than 6;

   Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 60 ring atoms.
2. The bipolar compound according to claim 1, wherein the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L may each independently comprise one or more of the following structural groups; combination:

   

   among them,

   X ¹ -X ¹² respectively represent CR ³ or N;

   Y is selected from N(R ⁴ ), C(R ⁴ R ⁵ ), Si(R ⁴ R ⁵ ), C(=O), S or O;

   R ³ represents H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, substituted or unsubstituted alkyl having 1 to 30 carbon atoms a substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom number of 5 to 60 aromatic hydrocarbon groups or an aromatic heterocyclic group;

   R ⁴ and R ⁵ each independently represent H, D, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom. The number is an aromatic hydrocarbon group or an aromatic heterocyclic group of 5 to 60.
3. The bipolar compound according to claim 1, wherein the Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , L each independently comprise one of the following chemical formulas, wherein the ring H can be arbitrarily replaced:

   

   
4. The bipolar compound according to claim 1, wherein the bipolar compound comprises a structure represented by any one of the formulae (2) to (6):

   
5. The bipolar compound according to any one of claims 1 to 5, wherein the bipolar compound is selected from one of the following structural formulae:

   

   
6. The bipolar compound according to any one of claims 1 to 5, wherein the bipolar compound has T ₁ ≥ 2.3 eV, and the T ₁ represents a triplet level of the bipolar compound.
7. A high polymer comprising at least one repeating unit comprising the structural unit represented by the chemical formula (1) according to claim 1.
8. A mixture comprising the bipolar compound according to any one of claims 1 to 6 or the high polymer according to claim 7, and at least one organic functional material, wherein the organic functional material may be selected from the following At least one of the materials: a hole injecting material hole transporting material, an electron transporting material electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, and an organic dye.
9. A composition comprising the bipolar compound of any one of claims 1 to 6 or the high polymer of claim 7, and at least one organic solvent.
10. An organic electronic device comprising the bipolar compound according to any one of claims 1 to 6 or the high polymer according to claim 7 or the mixture according to claim 8 or the composition according to claim 9. combination.
11. The organic electronic device according to claim 10, wherein said organic electronic device is an electroluminescent device, characterized in that said electroluminescent device comprises a functional layer, said functional layer comprising a device according to claims 1 to 6. A bipolar compound or a high polymer according to claim 7.
12. The organic electronic device according to claim 11, wherein the functional layer comprises a light-emitting layer and an electron transport layer, the light-emitting layer comprising a bipolar compound according to any one of claims 1 to 6. Or the high polymer according to claim 7, or the light emitting layer comprising the bipolar compound according to any one of claims 1 to 6 or the high polymer according to claim 7 and a phosphorescence The body, or the electron transport layer, comprises a bipolar compound according to any one of claims 1 to 6 or a high polymer according to claim 7.