JP5567660B2 - Deuterated compounds for luminescence applications - Google Patents

Description

Related Application Data This application is filed on US Provisional Patent Application No. 61 / 139,834, filed on May 22, 2009, filed on December 22, 2008, based on US Patent Act 119 (e). US Provisional Patent Application No. 61 / 176,141, which is incorporated herein by reference, the entire contents of both of which are incorporated herein by reference.

  The present invention relates to electroactive compounds that are at least partially deuterated. The invention also relates to an electronic device in which at least one active layer comprises such a compound.

  Organic electronic devices that emit light, such as light emitting diodes that make up displays, exist in many different types of electronic devices. In all such devices, an organic active layer is sandwiched between two electrical contact layers. The at least one electrical contact layer is light transmissive so that light can pass through the electrical contact layer. When electricity is applied to the electrical contact layer, the organic photoactive layer emits light that is transmitted through the light transmissive electrical contact layer.

  It is known that organic electroluminescent compounds are used as active components in light emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to exhibit electroluminescence. Semiconductor conjugated polymers have also been used as electroluminescent components, for example, U.S. Pat. No. 5,247,190, U.S. Pat. No. 5,408,109, and EP-A-443 861. Is disclosed.

  However, there is a continuing need for electroluminescent compounds.

  Provided is a compound selected from the group consisting of bis (diarylamino) anthracene and bis (diarylamino) chrysene having at least one D.

  There is also provided an electronic device comprising an active layer comprising the compound.

  Formula I or Formula II:

(Where:
R ¹ is the same or different for each occurrence, and is selected from the group consisting of D, alkyl, alkoxy, and aryl, and adjacent R ¹ groups combine to form a 5- or 6-membered aliphatic ring. You can,
Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of aryl groups;
a is the same or different each time it appears, and is an integer of 0 to 4,
b is the same or different each time it appears, and is an integer of 0 to 5,
There is at least one D)
Also provided is a compound represented by:

  There is also provided an electronic device comprising an active layer comprising a compound of formula I or formula II.

  In order to facilitate understanding of the concepts presented herein, embodiments are described in the accompanying drawings.

It is a figure of an example of an organic electronic device.

  As will be appreciated by those skilled in the art, the objects in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, in order to facilitate understanding of the embodiments, the dimensions of some objects in the drawings may be exaggerated more than other objects.

  Numerous aspects and embodiments are disclosed herein and are exemplary and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

  Other features and advantages of any one or more embodiments will be apparent from the following detailed description and from the claims. In this detailed description, the definitions and explanations of terms are dealt with first, followed by electroactive compounds, electronic devices, and finally examples.

1. Definitions and Explanations of Terms Before addressing details of embodiments described below, some terms are defined or explained.

  As used herein, the term “aliphatic ring” is intended to mean a cyclic group having no delocalized π electrons. In some embodiments, the aliphatic ring has no unsaturation. In some embodiments, the ring has one double or triple bond.

  The term “alkoxy” refers to the group RO—, where R is alkyl.

  The term “alkyl” is intended to mean a group derived from an aliphatic hydrocarbon having one point of attachment and includes linear, branched, or cyclic groups. The term is intended to include heteroalkyl and deuterated alkyl. The term is intended to include substituted and unsubstituted groups. The term “hydrocarbon alkyl” refers to an alkyl group having no heteroatoms. The term “deuterated alkyl” is a hydrocarbon alkyl having at least one available H substituted with D. In some embodiments, the alkyl group has 1-20 carbon atoms.

  The term “aryl” is intended to mean a group derived from an aromatic hydrocarbon having one point of attachment. The term “aromatic compound” is intended to mean an organic compound comprising at least one unsaturated cyclic group having delocalized π electrons. The term is intended to include heteroaryl and deuterated aryl. The term “hydrocarbon aryl” is intended to mean an aromatic compound having no heteroatoms in the ring. The term aryl includes groups having a single ring and groups having multiple rings which may be joined by a single bond or may be fused together. The term “deuterated aryl” refers to an aryl group in which at least one available H atom directly attached to aryl is replaced by D. The term “arylene” is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. Any suitable ring position of the aryl moiety can be covalently linked to the defined chemical structure. In some embodiments, the hydrocarbon aryl group has 3 to 60 carbon atoms, and in some embodiments, 6 to 30 carbon atoms. A heteroaryl group can have 3 to 50 carbon atoms, and in certain embodiments, can have 3 to 30 carbon atoms.

  The term “branched alkyl” means an alkyl group having at least one secondary or tertiary carbon. The term “secondary alkyl” means a branched alkyl group having a secondary carbon atom. The term “tertiary alkyl” means a branched alkyl group having a tertiary carbon atom. In certain embodiments, the branched alkyl group is attached via a secondary or tertiary carbon.

  When referred to in reference to a layer, material, member, or structure, the term “charge transport” refers to such layer, material, member, or structure such that the layer, material, member, or structure is relatively efficient and with low charge loss. It is intended to mean that it facilitates the movement of such charges through the thickness of the member, or structure. The hole transport material promotes a positive charge, and the electron transport material promotes a negative charge. A luminescent material may also have some charge transport properties, but the term “charge, hole, or electron transport layer, material, member, or structure” refers to a layer, material, member, Or is not intended to include structure.

  The term “compound” is intended to mean an uncharged material composed of molecules of atoms, where these atoms cannot be separated by physical means. When used to refer to a layer in a device, the phrase “adjacent” does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase “adjacent R groups” is used to mean R groups that are next to each other in a chemical formula (ie, multiple R groups present on multiple atoms joined by a single bond). The

  The term “deuteration” is intended to mean that at least one available H is replaced by D. A compound or group in which X% is deuterated has D substituted for X% of available H. A deuterated compound or group is a compound or group in which deuterium is present in at least 100 times its natural abundance.

  The term “electroactive” when referring to a layer or material is intended to mean a layer or material that electronically facilitates the operation of the device. Examples of active materials include materials that conduct, inject, transport, or block charge, which can be either electrons or holes, or emit radiation or electron-hole pairs when exposed to radiation. However, the present invention is not limited to these materials. Examples of inert materials include, but are not limited to, planarization materials, insulating materials, and environmental barrier materials.

  The prefix “hetero” indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the different atom is N, O, or S.

  The term “layer” is used interchangeably with the term “film” and refers to a coating covering a desired area. The term is not limited by size. This area may be the size of the entire device, a small special function area such as an actual visual display, or a small subpixel. Layers and films can be formed by any conventional deposition technique such as vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

  The term “organic electronic device” or sometimes simply “electronic device” is intended to mean a device comprising one or more organic semiconductor layers or organic semiconductor materials.

  The term “oxyalkyl” is intended to mean a heteroalkyl group in which one or more carbons are replaced with oxygen. The term includes groups that are bonded through oxygen.

The term “silyl” refers to the group R ₃ Si—, where R is H, D, C 1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are substituted with Si. In certain embodiments, the silyl group is (hexyl) ₂ Si (Me) CH ₂ CH ₂ Si (Me) ₂ — and [CF ₃ (CF ₂ ) ₆ CH ₂ CH ₂ ] ₂ SiMe—.

The term “siloxane” refers to the group (RO) ₃ Si—, where R is H, D, C 1-20 alkyl, or fluoroalkyl.

Unless otherwise specified, all groups may be substituted or unsubstituted. In certain embodiments, the substituent is selected from the group consisting of D, halide, alkyl, alkoxy, aryl, and cyano. Optional substituents such as, but not limited to, alkyl or aryl, may be substituted with one or more substituents that may be the same or different. Other suitable substituents include nitro, cyano, —N (R ′) (R ″), hydroxy, carboxy, alkenyl, alkynyl, aryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl , Siloxane, thioalkoxy, —S (O) ₂ —N (R ′) (R ″), —C (═O) —N (R ′) (R ″), (R ′) (R ″) N— Alkyl, (R ′) (R ″) N-alkoxyalkyl, (R ′) (R ″) N-alkylaryloxyalkyl, —S (O) _s -aryl (where s = 0 to 2), or -S (O) _s -heteroaryl (wherein s = 0 to 2). Each of R ′ and R ″ is independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R ′ and R ″ and they are Together with the binding nitrogen, it can form a ring system. The substituent may be a crosslinking group. As used herein, the terms “comprising”, “comprising”, “including”, “including”, “having”, “having”, or any other variation thereof, It is intended to handle exclusive inclusion. For example, a process, method, article, or apparatus that includes a set of elements is not necessarily limited to only those elements, and is not explicitly or inherently related to such a process, method, article, or apparatus. But other elements can be included. Further, unless otherwise specified, “or” means inclusive, not exclusive, or. For example, the condition A or B is satisfied by any one of the following. That is, A is true (or present) B is false (or absent), A is false (or absent) B is true (or exists), and A and B Both are true (or exist).

  “A” or “an” is also used to describe elements and components of the present invention. This is merely for convenience and is done to provide a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used to practice or test embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

In addition, the IUPAC numbering scheme is used throughout, and periodic table families are numbered from 1 to 18 from left to right (CRC Handbook of Chemistry and Physics, 81 ^st Edition, 2000).

2. Electroactive compounds The compounds described herein are bis (diarylamino) anthracenes or bis (diarylamino) chrysene having at least one D. In some embodiments, the compounds of the invention are at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% Deuterated, in some embodiments at least 40% deuterated, in some embodiments at least 50% deuterated, in some embodiments at least 60% Are deuterated, in some embodiments at least 70% deuterated, in some embodiments at least 80% deuterated, and in some embodiments at least 90% deuterated. % Is deuterated.

  In certain embodiments, the electroactive compounds of the present invention have Formula I or Formula II:

(Where:
R ¹ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, and aryl, and adjacent R ¹ groups are bonded to form a 5- or 6-membered aliphatic ring. You may,
Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of aryl groups;
a is the same or different each time it appears, and is an integer of 0 to 4,
b is the same or different each time it appears, and is an integer of 0 to 5)
This compound has at least one D.

  In certain embodiments, the compounds of the present invention are capable of emitting red, green, or blue light.

  In certain embodiments of Formulas I and II, deuteration is performed on a substituent on the aryl ring. The aryl group having a deuterated substituent may be a core anthracene group of formula I or a core chrysene group of formula II, or an aryl on nitrogen, or an aryl group of the substituent can be. In some embodiments, the deuterated substituent on the aryl ring is selected from alkyl, aryl, alkoxy, and aryloxy. In some embodiments, the substituents are at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterium. In some embodiments, at least 40% is deuterated, in some embodiments, at least 50% is deuterated, and in some embodiments, at least 60% is deuterated. Hydrogenated, in some embodiments at least 70% deuterated, in some embodiments at least 80% deuterated, and in some embodiments at least 90% Deuterated.

In certain embodiments of Formulas I and II, deuteration is performed on any one or more of the aryl groups Ar ¹ to Ar ⁴ . In this case, at least one of Ar ¹ to Ar ⁴ is a deuterated aryl group. In some embodiments, Ar ¹ to Ar ⁴ are at least 10% deuterated. This means that at least 10% of all available H bound to aryl C in Ar ¹ to Ar ⁴ is replaced with D. In some embodiments, each aryl ring has several Ds. In some embodiments, some but not all aryl rings have D. In some embodiments, Ar ¹ to Ar ⁴ are at least 20% deuterated, in some embodiments at least 30% deuterated, and in some embodiments at least 40%. Is deuterated, in some embodiments at least 50% deuterated, in some embodiments at least 60% deuterated, and in some embodiments at least 70%. % Is deuterated, in some embodiments at least 80% is deuterated and in some embodiments at least 90% is deuterated.

  In certain embodiments of Formulas I and II, deuteration is performed on both substituents and aryl groups.

  In some embodiments, the compounds of Formulas I and II are at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30 % Is deuterated, in some embodiments at least 40% is deuterated, in some embodiments at least 50% is deuterated, and in certain embodiments at least 60% is deuterated, in some embodiments at least 70% deuterated, in some embodiments at least 80% deuterated, in some embodiments, At least 90% is deuterated.

  In some embodiments of Formula I, both a = 0.

In some embodiments of Formula I, at least one a is greater than 0. In some embodiments, at least one R ¹ is a hydrocarbon alkyl. In certain embodiments, R ¹ is deuterated alkyl. In some embodiments, R ¹ is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.

In some embodiments of Formula I, both a = 4 and R ¹ is D.

In Formula II, the bond to (R ¹ ) _a is intended to indicate that the R ¹ group can be in any position on the two fused rings.

  In some embodiments of Formula II, both b = 0.

In some embodiments of Formula II, at least one b is greater than zero. In some embodiments, at least one R ¹ is a hydrocarbon alkyl. In some embodiments, R ¹ is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.

In some embodiments of Formula II, both b = 5 and R ¹ is D.

In certain embodiments, at least one of Ar ¹ to Ar ⁴ is represented by formula III:

(Where:
R ² is the same or different each time it appears, and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyl, and siloxane, or adjacent R ² groups are bonded to form an aromatic ring. Can be
c is the same or different each time it appears, and is an integer of 0 to 4,
d is the same or different each time it appears, and is an integer of 0 to 5,
m is the same or different each time it appears, and is an integer of 0 to 6)
It is represented by

In certain embodiments, at least one of Ar ¹ to Ar ⁴ is represented by formula IV:

(Where:
R ² is the same or different for each occurrence, and is selected from the group consisting of D, alkyl, alkoxy, and aryl, or can adjacent R ² groups be bonded to form an aromatic ring? And
c is the same or different each time it appears, and is an integer of 0 to 4,
d is the same or different each time it appears, and is an integer of 0 to 5,
m is the same or different each time it appears, and is an integer of 0 to 6)
It is represented by

In some embodiments, Ar ¹ to Ar ⁴ are selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, and binaphthyl.

In some embodiments, Ar ¹ to Ar ⁴ are perdeuterated.

In certain embodiments, Ar ¹ to Ar ⁴ are perdeuterated except for one alkyl group on the terminal aryl.

In certain embodiments, the compounds of the invention are symmetric with respect to the diarylamino group. In this case, Ar ¹ = Ar ³ and Ar ² = Ar ⁴ .

In certain embodiments, the compounds of the invention are asymmetric with respect to the diarylamino group. In this case, Ar ¹ is different from both Ar ³ and Ar ⁴ . In some embodiments, Ar ² is also different from both Ar ³ and Ar ⁴ .

Some non-limiting examples of compounds of formula I include the following compounds E1 and E2.
Compound E1:

Compound E2:

Some non-limiting examples of compounds represented by Formula II include the following compounds E3-E9.
Compound E3:

Compound E4:

Compound E5:

Compound E6:

Compound E7:

Compound E8:

E9:

  Non-deuterated analogs can be made using any technique that results in a C—C bond or a C—N bond. A variety of such techniques are well known, such as Suzuki coupling, Yamamoto coupling, Stille coupling, Pd-catalyzed or Ni-catalyzed CN coupling. The novel deuterated compounds of the present invention can then be prepared by analogous methods using deuterated precursor materials or, more generally, Lewis acids H /, such as aluminum trichloride or ethylaluminum chloride. It can be prepared by treating a non-deuterated compound with a deuterated solvent such as d6-benzene in the presence of a D-exchange catalyst. Typical manufacture is shown in the examples. The degree of deuteration can be determined by mass spectrometry such as NMR analysis and atmospheric pressure solid analysis probe mass spectrometry (ASAP-MS).

  The compounds described herein can be formed into films using liquid deposition techniques. Surprisingly and unexpectedly, these compounds have greatly improved properties compared to similar non-deuterated compounds. Electronic devices that include an active layer having a compound described herein have a greatly improved lifetime. Furthermore, this increase in lifetime is achieved with high quantum efficiency and good saturation. Furthermore, the deuterated compounds described herein have a higher air resistance than non-deuterated analogs. Thereby, better processing tolerance can be obtained both in the production and purification of the material and in the formation of electronic devices using the material.

  The novel deuterated compounds described herein are useful as hole transport materials, as electroluminescent materials, and as hosts for electroluminescent materials.

3. Electronic devices Organic electronic devices that may benefit from having one or more layers comprising the electroluminescent materials described herein include (1) devices that convert electrical energy into radiation (eg, light emitting diodes, light emitting diodes). (Displays or diode lasers), (2) devices that detect signals through electronic processes (eg, photodetectors, photoconductive cells, photoresistors, optical switches, phototransistors, phototubes, IR detectors), (3 ) Devices that convert radiation into electrical energy (eg, photovoltaic devices or solar cells), and (4) devices that include one or more electronic components (eg, transistors or diodes) that include one or more organic semiconductor layers. However, it is not limited to these.

  An example of an organic electronic device structure is shown in FIG. The device 100 has an anode layer 110 of a first electrical contact layer, a cathode layer 160 of a second electrical contact layer, and an electroactive layer 140 therebetween. There is a buffer layer 120 adjacent to the anode. Adjacent to the buffer layer is a hole transport layer 130 that includes a hole transport material. There may be an electron transport layer 150 comprising an electron transport material adjacent to the cathode. As one option, the device may include one or more additional hole injection or hole transport layers (not shown) next to the anode 110 and / or one or more additional electrons next to the cathode 160. An injection layer or an electron transport layer (not shown) can be used.

  Layers 120-150 are individually and collectively referred to as the active layer.

  In one embodiment, the various layers have a thickness in the following range. Anode 110, 500-5000Å, in one embodiment 1000-2000Å, buffer layer 120, 50-2000Å, in one embodiment 200-1000Å, hole transport layer 130, 50-2000Å, in one embodiment 200- 1000Å, electroactive layer 140, 10-2000Å, in one embodiment 100-1000Å, layer 150, 50-2000Å, in one embodiment 100-1000Å, cathode 160, 200-10000Å, in one embodiment 300- 5000kg. The location of the electron-hole recombination region in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. The desired ratio of layer thickness depends on the exact nature of the material used.

  Depending on the application of the device 100, the electroactive layer 140 is a light emitting layer (such as in a light emitting diode or light emitting electrochemical cell) that is excited by an applied voltage, responsive to radiant energy, using bias voltage application or It may be a material layer (such as in a photodetector) that generates a signal without being used. Examples of photodetectors include photoconductive cells, photoresistors, optical switches, phototransistors, and phototubes, and photovoltaic cells, these terms are Markus, John, Electronics and Nucleonics Dictionaries, 470 and 476. (McGraw-Hill, Inc. 1966).

  In certain embodiments, the novel deuterated compounds of the present invention are useful as hole transport materials in layer 130. In certain embodiments, at least one additional layer includes a deuterated material. In some embodiments, the additional layer is a hole injection layer 120. In some embodiments, the additional layer is an electroactive layer 140. In some embodiments, the additional layer is an electron transport layer 150.

  In certain embodiments, the novel deuterated compounds of the present invention are useful as host materials for electroactive materials in electroactive layer 140. In some embodiments, the luminescent material is also deuterated. In certain embodiments, at least one additional layer includes a deuterated material. In some embodiments, the additional layer is a buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electron transport layer 150.

  In certain embodiments, the novel deuterated compounds of the present invention are useful as electroactive materials in electroactive layer 140. In some embodiments, a host is also present in the electroactive layer. In some embodiments, the host material is also deuterated. In certain embodiments, at least one additional layer includes a deuterated material. In some embodiments, the additional layer is a buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electron transport layer 150.

  In some embodiments, the novel deuterated compounds of the present invention are useful as electron transport materials in layer 150. In certain embodiments, at least one additional layer includes a deuterated material. In some embodiments, the additional layer is a buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electroactive layer 140.

  In certain embodiments, the electronic device has a deuterated material of any combination of layers selected from the group consisting of a buffer layer, a hole transport layer, an electroactive layer, and an electron transport layer.

  In certain embodiments, the devices of the present invention have additional layers to facilitate processing or to improve functionality. Any or all of these layers can include a deuterated material. In some embodiments, all organic device layers include a deuterated material. In some embodiments, all organic device layers consist essentially of deuterated material.

a. Electroactive Layer The novel deuterated compounds described herein are useful as electroactive materials in layer 140. The compound of the present invention can be used alone or in combination with a host material.

  In some embodiments, the electroactive layer consists essentially of the host material and the novel deuterated compounds described herein.

  In some embodiments, the host is a bis-fused cyclic aromatic compound.

In some embodiments, the host is an anthracene derivative compound. In some embodiments, the compound has the following formula:
An-L-An
(Where:
An is an anthracene moiety,
L is a divalent linking group)
It is represented by

In certain embodiments of this formula, L is a single bond, —O—, —S—, —N (R) —, or an aromatic group. In some embodiments, An is a mono- or diphenylanthryl moiety.

In some embodiments, the host has the formula:
A-An-A
(Where:
An is an anthracene moiety,
A is the same or different for each occurrence, and is an aromatic group)
It is represented by

  In certain embodiments, the A group is attached to the 9 or 10 position of the anthracene moiety. In some embodiments, A is selected from the group consisting of naphthyl, naphthylphenylene, and naphthylnaphthylene. In some embodiments, the compound is symmetric, and in some embodiments, the compound is asymmetric.

  In some embodiments, the host has the formula:

(Where:
A ¹ and A ² are the same or different for each occurrence, and are selected from the group consisting of H, an aromatic group, an alkyl group, and an alkenyl group, or A represents one or more complex aromatic rings Can
p and q are the same or different and are integers of 1 to 3)
It is represented by

  In some embodiments, the anthracene derivative is asymmetric. In some embodiments, p = 2 and q = 1.

In some embodiments, at least one of A ¹ and A ² is a naphthyl group. In some embodiments, additional substituents are present.

  In some embodiments, the host is

And a group consisting of combinations thereof.

  In addition to being useful as electroactive materials in electroactive layers, the novel deuterated compounds described herein function as charge carrier hosts for other electroactive materials in electroactive layer 140. You can also In some embodiments, the electroactive layer consists essentially of the novel deuterated material of the present invention and one or more electroactive electroactive materials.

b. Other Device Layers The other layers in the device may be made of any material known to be useful in such layers.

  The anode 110 is an electrode that is particularly effective for injecting positive charge carriers. The anode may be made of a material containing, for example, a metal, mixed metal, alloy, metal oxide, or mixed metal oxide, or may be a conductive polymer, and mixtures thereof. Suitable metals include Group 11 metals, Group 4-6 metals, and Group 8-10 transition metals. Where the anode is to be light transmissive, mixed metal oxides of Group 12, 13, and 14 metals such as indium tin oxide are commonly used. The anode 110 can also include organic materials such as polyaniline as described in “Flexible light-emitting diodes from solid conducting polymer”, Nature Vol. 357, pp 477-479 (June 11, 1992). . Desirably, at least one of the anode and the cathode is at least partially transparent so that the generated light can be observed.

  The buffer layer 120 includes a buffer material and includes, but is not limited to, planarization of the underlying layer, charge transport and / or charge injection properties, trapping of impurities such as oxygen or metal ions, and performance of organic electronic devices. One or more functions may be included in the organic electronic device, such as other features that facilitate or improve. The buffer material may be a polymer, oligomer, or small molecule. They can be vapor deposited or deposited from a liquid that may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

  The buffer layer can be formed of a polymer material such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is often doped with protonic acid. The protic acid may be, for example, poly (styrene sulfonic acid), poly (2-acrylamido-2-methyl-1-propane sulfonic acid) and the like.

  The buffer layer can include a charge transport compound such as copper phthalocyanine or tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ).

  In some embodiments, the buffer layer includes at least one conductive polymer and at least one fluorinated acid polymer. Such materials are described, for example, in U.S. Patent Application Publication No. 2004-0102577, U.S. Patent Application Publication No. 2004-0127637, and U.S. Patent Application Publication No. 2005/205860.

  In some embodiments, the novel deuterated compounds described herein are useful as hole transport materials. Examples of other hole transport materials of layer 130 are, for example, Y. Wang, Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 18, p. 837-860, 1996. Both hole transport molecules and hole transport polymers can be used. Commonly used hole transport molecules are N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD), 1 , 1-Bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N′-bis (4-methylphenyl) -N, N′-bis (4-ethylphenyl)-[1,1 ′ -(3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA), a-phenyl 4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4 (N, N-diethylamino) 2-methylphenyl] (4-methylphenyl) methane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP), 1, 2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ′, N′tetrakis (4-methylphenyl)-(1,1′-biphenyl) -4,4′- Porphyrin compounds such as diamine (TTB), N, N′-bis (naphthalen-1-yl) -N, N′-bis- (phenyl) benzidine (α-NPB), and copper phthalocyanine. Commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl) polysilane, and polyaniline. Hole transport polymers can also be obtained by doping hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers, in particular triarylamine-fluorene copolymers, are used. In some cases, these polymers and copolymers are crosslinkable. Examples of crosslinkable hole transporting polymers can be found in, for example, US Patent Application Publication No. 2005-0184287 and WO 2005/052027. In some embodiments, the hole transport layer is a p-dopant such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride. Doped with.

In some embodiments, the novel deuterated compounds described herein are useful as electron transport materials. Examples of other electron transport materials that can be used in layer 150 include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq ₃ ), bis (2-methyl-8-quinolinolato) (p -Phenyl-phenolato) aluminum (III) (BAlQ) and 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD) and 3- (4 -Biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI) Azole compounds such as 2,3-bis (4-fluorophenyl) quinoxaline, quinoxaline derivatives such as 9,10-diphenylphena Tororin (DPA) and 2,9-dimethyl-4,7-phenanthroline derivatives such as diphenyl-1,10-phenanthroline (DDPA), and mixtures thereof. The electron transport layer can also be doped with n-dopants such as Cs or other alkali metals. Layer 150 can serve both as a buffer or confinement layer that promotes electron transport and prevents exciton quenching at the layer interface. Preferably, this layer promotes electron transfer and reduces exciton quenching.

The cathode 160 is an electrode that is particularly effective for injecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. The cathode material can be selected from Group 1 alkali metals (eg, Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals, such as rare earth elements and lanthanides, and actinides. Aluminum, indium, calcium, barium, samarium, and magnesium, and combinations of materials can be used. Li or Cs-containing organometallic compounds, LiF, CsF, and Li ₂ O can also be deposited between the organic layer and the cathode layer to reduce the operating voltage.

  It is known to have another layer in an organic electronic device. For example, to control the amount of positive charge injected and / or promote layer bandgap integrity, or to act as a protective layer, a layer (see FIG. (Not shown) may be present. Layers well known in the art can be used, such as copper phthalocyanines, silicon oxynitrides, fluorocarbons, silanes, or ultrathin layers of metals such as Pt. Alternatively, the anode layer 110, the active layers 120, 130, 140, and 150, or some or all of the cathode layer 160 can be surface treated to increase charge carrier transport efficiency. The choice of material for each constituent layer is preferably determined by balancing the positive and negative charges in the light emitting layer to obtain a device with high electroluminescence efficiency.

  It should be understood that each functional layer may be composed of more than one layer.

  The devices of the present invention can be made by a variety of techniques such as sequential vapor deposition of individual layers on a suitable substrate. Substrates such as glass, plastic, and metal can be used. Conventional vapor deposition techniques such as thermal evaporation and chemical vapor deposition can be used. Alternatively, the organic layer can be a suitable solvent using conventional coating or printing techniques such as, but not limited to, spin coating, dip coating, roll-to-roll techniques, inkjet printing, screen printing, gravure printing, etc. It can also be applied from solutions or dispersions therein.

  In order to realize a high-efficiency LED, it is desirable that the HOMO (highest occupied molecular orbital) of the hole transport material is matched with the work function of the anode, and the LUMO (lowest molecular orbital) of the electron transport material is the cathode work function. It is desirable to be adapted to Material chemical compatibility and sublimation temperature are also important considerations in the selection of electron and hole transport materials.

  It should be understood that the efficiency of devices made using the chrysene compounds described herein can be further improved by optimizing other layers in the device. For example, more efficient cathodes such as Ca, Ba, or LiF can be used. Molded substrates and novel hole transport materials that lower the operating voltage and increase quantum efficiency are also available. Additional layers can be added to adjust the energy levels of the various layers and promote electroluminescence.

  The chrysene compounds of the present invention are often fluorescent and photoluminescent and can be useful in applications other than OLEDs, such as oxygen sensitive indicators and fluorescent indicators in bioassays.

  The following examples illustrate certain features and advantages of the present invention. These are intended to illustrate the present invention and are not intended to be limiting. Unless otherwise specified, all percentage values are based on weight.

Comparative Example A
This example demonstrates the preparation of Comparative Example Compound A, which is a non-deuterated electroluminescent material.

(A) Production of 1- (4-tert-butylstyryl) naphthalene.
An oven-dried 500 ml three-necked round bottom flask was equipped with a magnetic stir bar, addition funnel, and nitrogen inlet connector. The flask was charged with (1-naphthylmethyl) triphenylphosphonium chloride (12.07 g, 27.5 mmol) and 200 ml of anhydrous THF. Sodium hydride (1.1 g, 25 mmol) was added in one portion. The mixture became bright orange and was stirred at room temperature overnight. A solution of 4-tert-butyl-benzaldehyde (7.1 g, 25 mmol) in anhydrous THF (30 ml) was added to the addition funnel using a cannula. This aldehyde solution was added dropwise to the reaction mixture over 45 minutes. The reaction was stirred at room temperature for 24 hours (orange color disappeared). Silica gel was added to the reaction mixture and volatiles were removed under reduced pressure. The resulting crude product was purified by column chromatography on silica gel using 5-10% dichloromethane in hexane. The product was isolated as a mixture of cis and trans isomers (6.3 g, 89%) and used without separation. ^The structure was confirmed by ¹ H NMR.

(B) Production of 3-tert-butylchrysene.
1- (4-tert-butylstyryl) naphthalene (4.0 g, 14.0 mmol) was dissolved in dry toluene (1 l) in a 1 liter photochemical vessel fitted with a nitrogen inlet and a stir bar. After the dry propylene oxide bottle was cooled in ice water, 100 ml of epoxide was withdrawn with a syringe and added to the reaction mixture. Finally iodine (3.61 g, 14.2 mmol) was added. A cooler was attached to the photochemical vessel, and a halogen lamp (Hanovia, 450 W) was turned on. When no disappearance of iodine in the reaction mixture became apparent from the disappearance of the color, the lamp was turned off to stop the reaction. The reaction was completed in 3.5 hours. Removal of toluene and excess propylene oxide under reduced pressure gave a dark yellow solid. The crude product was dissolved in a small amount of 25% dichloromethane in hexane, passed through a 4 inch plug of neutral alumina and washed with 25% dichloromethane in hexane (about 1 liter). Removal of volatiles gave 3.6 g (91%) of 3-tert-butylchrysene as a yellow solid. ^The structure was confirmed by ¹ H NMR.

(C) Preparation of 6,12-dibromo-3-tert-butylchrysene 3-tert-Butylchrysene (4.0 g, 14.1 mmol) and trimethyl phosphate (110 ml) were mixed in a 500 ml round bottom flask. After adding bromine (4.95 g, 31 mmol), the flask was equipped with a reflux condenser and the reaction mixture was stirred in an oil bath at 105 ° C. for 1 hour. A white precipitate formed almost immediately. The reaction mixture was worked up by pouring onto a small amount of ice water (100 ml). The mixture was filtered under reduced pressure and washed thoroughly with water. The resulting tan solid was dried under vacuum. The crude product was boiled in methanol (100 ml), cooled to room temperature and filtered again to give 3.74 g (60%) of a white solid. ^The structure was confirmed by ¹ H NMR.

(D) Production of 3-tert-butyl-N ⁶ , N ⁶ , N ¹² , N ¹² -tetraphenylchrysene-6,12-diamine as Comparative Example Compound A 6,12-dibromo-3 in a dry box -Tert-butyl chrysene (0.8 g, 1.81 mmol) and diphenylamine (1.22 g, 7.2 mmol) were placed in a 500 ml round bottom flask and dissolved in 10 ml of dry toluene. 2-biphenyl-di-tert-butylphosphine (0.072 g, 0.04 mmol) and tris (dibenzylideneacetone) dipalladium (0) (0.036 g, 0.02 mmol) were dissolved in 5 ml of dry toluene, Stir for 10 minutes. This catalyst solution was added to the reaction mixture and stirred for 10 minutes, followed by sodium tert-butoxide (0.35 g, 3.62 mmol) and 5 ml of dry toluene. After another 10 minutes, the reaction flask was removed from the dry box, attached to a nitrogen line and stirred at 110 ° C. overnight. The next day, the reaction mixture was cooled to room temperature, filtered through a 2 inch plug of silica gel and Celite and washed with 500 ml of dichloromethane. Removal of volatiles under reduced pressure gave a dark brown oil. The crude product was further purified by flash chromatography on silica gel using an Isolera purification system from Biotage. The resulting solid was washed with methanol and then recrystallized from hot hexane to give 0.26 g (25%) of product. ^The structure was confirmed by ¹ H NMR.

Example 1
This example illustrates the preparation of compound E3, a compound of formula II.

This compound was prepared from 6,12-dibromo-3-tert-butylchrysene and di (perdeuterophenyl) amine using the procedure described above for Comparative Compound A. Yield 0.37 g (36%). The structure of Compound E3 was confirmed by ¹ H NMR.

Comparative Example B
This example shows the preparation of Comparative Example Compound B, which is a non-deuterated electroluminescent material.

In a round bottom flask in a nitrogen-filled glove box, 0.45 g 2,6-di-tert-butyl-9,10-dibromoanthracene (1 mM) (Mue, U .; Adam, M .; Mullen, K. Chem. Ber. 1994, 127, 437-444) and 0.38 g (2.2 mM) diphenylamine and 0.2 g sodium tert-butoxide (2 mM) were added along with 40 mL of toluene. 0.15 g Pd ₂ DBA ₃ (0.15 mM) and 0.07 g P (t-Bu) 3 (0.3 mM) were dissolved in 10 mL toluene and added to the first solution with stirring. When all ingredients are mixed, the solution slowly exotherms and turns tan. This solution was heated and stirred under nitrogen at 80 C in a glove box for 1 hour. The solution immediately becomes dark purple, but when it reaches about 80 C, it becomes dark yellow-green and exhibits marked green luminescence. After cooling to room temperature, the solution was removed from the glove box, filtered through a short basic alumina plug and eluted using toluene, resulting in a bright yellow-green band. Evaporation and recrystallization from toluene / methanol gave the expected product as confirmed by 1-H nmr in 0.55 g yield.

Example 2
This example illustrates the preparation of compound E1, a compound of formula I.

This compound was prepared from 9,10-dibromo-2,6 di-tert-butylanthracene and di (perdeuterophenyl) amine using the procedure described above for Comparative Compound B. Yield 0.55g. The structure of Compound E1 was confirmed by ¹ H NMR.

Example 3 and Comparative Example C
These examples illustrate the manufacture and performance of devices with blue light emitters. The following materials were used.

The device had the following structure on a glass substrate.
Anode = Indium tin oxide (ITO): 50 nm
Buffer layer = Buffer 1 (50 nm), which is an aqueous dispersion of conductive polymer and polymeric fluorinated sulfonic acid. Such materials are described, for example, in U.S. Patent Application Publication No. 2004/0102577, U.S. Patent Application Publication No. 2004/0127637, and U.S. Patent Application Publication No. 2005/0205860.

Hole transport layer = polymer P1 (20 nm)
Electroactive layer = 13: 1 host H1: dopant (40 nm)
Electron transport layer = metal quinolate derivative (10 nm)
Cathode = CsF / Al (0.7 / 100 nm)

  The OLED device was manufactured by a combination of solution processing and thermal evaporation techniques. A glass substrate coated with patterned indium tin oxide (ITO) from Thin Film Devices, Inc was used. These ITO substrates are based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohm / square and 80% light transmission. These patterned ITO substrates were ultrasonically cleaned in an aqueous detergent solution and rinsed with distilled water. The patterned ITO was then ultrasonically cleaned in acetone, rinsed with isopropanol, and dried in a stream of nitrogen.

  Immediately prior to device fabrication, the patterned ITO substrate was washed with UV ozone for 10 minutes. Immediately after cooling, an aqueous dispersion of Buffer 1 was spin coated on the ITO surface and heated to remove the solvent. After cooling, the substrate was then spin coated with a solution of hole transport material and heated to remove the solvent. After cooling, the substrate was spin-coated with the luminescent layer solution and heated to remove the solvent. The substrate was masked and placed in a vacuum chamber. An electron transport layer was deposited by thermal evaporation, followed by a CsF layer. The mask was then changed under vacuum and an Al layer was deposited by thermal evaporation. The vacuum chamber was vented and the device was encapsulated using a glass lid, desiccant, and UV curable epoxy.

  OLED samples were characterized by measuring their (1) current-voltage (IV) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectrum versus voltage. All three measurements were made simultaneously and controlled by a computer. By dividing the electroluminescent radiance of the LED by the current density required to operate the device, the current efficiency of the device at a certain voltage is determined. This unit is cd / A. The output efficiency is a value obtained by dividing the current efficiency by the operating voltage. This unit is lm / W. Device data is shown in Table 1.

  The relative lifetime of the device made using the chrysene dopant of formula II is much better than the device made using Comparative Compound A.

Example 4 and Comparative Example D
These examples illustrate the manufacture and performance of devices with green light emitters.

The device had the following structure on a glass substrate.
Anode = ITO (180nm)
Buffer layer = Buffer 1 (50 nm)
Hole transport layer = polymer P1 (20 nm)
Electroactive layer = 13: 1 host H1: dopant (60 nm)
Electron transport layer = metal quinolate derivative (10 nm)
Cathode = CsF / Al (1.0 / 100 nm)

  An OLED device was fabricated as described above in Example 3. Device data (average of 3 devices) is shown in Table 2.

  The relative lifetime of a device made using the anthracene dopant of formula I is far superior to a device made using Comparative Compound B, which is an anthracene dopant.

  Not all acts described above in the summary or example are required and some of the specific acts may not be necessary, and one or more additional actions may be performed in addition to the actions described above Note that there may be cases. Further, the order in which actions are listed are not necessarily the order in which they are performed.

  In the foregoing specification, the concepts of the invention have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, any or all of these benefits, advantages, solutions to problems, and any features that may generate or make any benefit, advantage, or solution appear to be any or all of the claims Should not be construed as an important, necessary, or essential feature of.

  It should be understood that in the context of separate embodiments, the specific features described herein for clarity may be provided in combination in one embodiment. Conversely, the various features described in the context of one embodiment for the sake of brevity can also be provided separately or in any sub-combination. Furthermore, references to values within a range include all values within that range.

Claims (12)

Formula I or Formula II:

(Where:
R ¹ is the same or different for each occurrence, and is selected from the group consisting of D, hydrocarbon alkyl, deuterated alkyl, and adjacent R ¹ groups are bonded to form a 5- or 6-membered aliphatic ring. May form,
Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of an aryl group, and the aryl group optionally has at least one substituent on the aryl ring; The aryl group may include heteroaryl,
The substituent is D, halide, alkyl, alkoxy, aryl, cyano, nitro, —N (R ′) (R ″), hydroxy, carboxy, alkenyl, alkynyl, aryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoro. Alkoxy, arylalkyl, silyl, siloxane, thioalkoxy, -S (O) _2- N (R ') (R "), -C (= O) -N (R') (R"), (R ') (R ″) N-alkyl, (R ′) (R ″) N-alkoxyalkyl, (R ′) (R ″) N-alkylaryloxyalkyl, —S (O) _s -aryl, where s = 0-2), and -S (O) _s -heteroaryl (where s = 0-2),
Each of R ′ and R ″ is independently an optionally substituted alkyl, cycloalkyl, or aryl group;
R ′ and R ″ may be combined with the nitrogen to which they are attached to form a ring system;
The substituent may be a crosslinking group,
a is the same or different each time it appears, and is an integer from 1 to 4, and
b is the same or different each time it appears and is an integer from 1 to 5, and has at least one D. The compound of claim 1, wherein at least 50% is deuterated. Have at least one substituent on at least one aryl ring of Ar ⁴ from the Ar ^1,
3. A compound according to claim 1 or 2 , wherein deuteration is carried out on at least one of the substituents. The compound according to claim 1 or 2 , wherein at least one of Ar ¹ to Ar ⁴ is a deuterated aryl group. From Ar ¹ Ar ² is at least 20% deuterated compound according to claim 4. Have at least one substituent on at least one aryl ring of Ar ⁴ from the Ar ^1,
At least one of said deuterated on both substituents and at least one of the aryl ring is being performed, the compound according to claim 1 or 2. The compound according to claim 1 or 2 , wherein R ¹ is a hydrocarbon alkyl. The compound according to claim 1 or 2 , wherein R ¹ is deuterated alkyl. 3. A compound according to claim 1 or 2 represented by formula I, wherein a = 4 and R < ¹ > is D. 3. A compound according to claim 1 or 2 represented by formula II, wherein b = 5 and R < ¹ > is D. Ar ¹ to Ar ⁴ are naphthyl, phenylnaphthyl , naphthylphenyl, binaphthyl, and Formula III:

(Where:
R ² is the same or different each time it appears, and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyl, and siloxane, or adjacent R ² groups are bonded to form an aromatic ring. Can be
c is the same or different each time it appears, and is an integer of 0 to 4,
d is the same or different each time it appears, and is an integer of 0 to 5,
m is the same or different each time it appears, and is an integer of 0 to 6)
The compound of Claim 1 or 2 selected from the group which consists of group represented by these. The compound according to claim 1 or 2 , wherein Ar ¹ to Ar ⁴ are perdeuterated.

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