CN117624209A

CN117624209A - Organic electroluminescent material and device

Info

Publication number: CN117624209A
Application number: CN202311078669.8A
Authority: CN
Inventors: T·费利塔姆; J·费尔德曼; 亚力克西·鲍里索维奇·迪亚特金; 马斌
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2022-08-26
Filing date: 2023-08-25
Publication date: 2024-03-01

Abstract

The application relates to organic electroluminescent materials and devices. Provided is an organic compound comprising the structure: wherein the two 6-membered aromatic rings are connected with a direct bond and are further connected by a linking group selected from the group consisting of: o, S, se; NR, BR, BRR ', PR, CR, c= O, C =nr, c=crr ', c= S, CRR ', SO ₂ P (O) R, siRR 'and GeRR'. Formulations comprising these organic compounds are also provided. Further provided are organic light emitting device OLEDs and related consumer products utilizing these organic compounds.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application claims priority from U.S. c. ≡119 (e) U.S. provisional application No. 63/373,564, filed on 8/26 of 2022, the entire contents of which are incorporated herein by reference. The present application further claims priority from U.S. c. ≡119 (e) U.S. provisional application No. 63/488,769 filed on 7/3 at 2023, the entire contents of which are incorporated herein by reference.

Technical Field

The present disclosure relates generally to organometallic compounds and formulations and various uses thereof, including as hosts or emitters in devices such as organic light emitting diodes and related electronic devices.

Background

Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to fabricate the devices are relatively inexpensive, so organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting.

One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color (referred to as a "saturated" color). In particular, these standards require saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In conventional liquid crystal displays, the emission from a white backlight is filtered using an absorbing filter to produce red, green and blue emissions. The same technique can also be used for OLEDs. The white OLED may be a single emissive layer (EML) device or a stacked structure. The colors may be measured using CIE coordinates well known in the art.

Disclosure of Invention

In one aspect, the present disclosure provides a compound of formula I:

wherein X is ¹ -X ⁸ Each independently is C or N;

wherein Y is ^A Selected from the group consisting of: o, S, se; NR, BR, BRR ', PR, CR, c= O, C =nr, c=crr ', c= S, CRR ', SO ₂ P (O) R, siRR 'and GeRR';

wherein each R is ^A Independently represents a single substitution to the maximum possible number of substitutions or no substitution;

wherein each R is ^A R and R' are independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

wherein the compound comprises at least one biscarbazolyl group and at least one silyl group; and is also provided with

Wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, at least one of the following conditions is true:

1)X ¹ -X ⁸ at least one of (a)Each is N and R ^A At least one of which is a substituted biscarbazolyl group comprising silane;

2)Y ^A Is NR and R ^A At least one of which is a substituted biscarbazolyl group comprising silane;

3)R ^A is a carbazole moiety substituted with at least one group comprising silane and at least one substituted or unsubstituted carbazole;

4)X ¹ -X ⁸ each is C and X ¹ -X ⁴ At least one of the groups-L-SiAr ¹ Ar ² Ar ³ Substituted and X ¹ -X ⁸ At least one of the warp groups NR ⁵ R ⁶ Substitution; provided that if Y ^A Is O and X ⁴ Through SiPh ₃ Substituted, then X ⁵ -X ⁸ One of which is NR via said group ⁵ R ⁶ Substitution;

wherein each Ar is ¹ 、Ar ² And Ar is a group ³ Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

wherein each R is ⁵ And R is ⁶ Independently is an optionally further substituted 5-or 6-membered aromatic or heteroaromatic ring;

wherein L is a direct bond or a substituted or unsubstituted aryl or heteroaryl group;

wherein if L is aryl, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

Wherein if X ² -X ⁴ One of them is via-L-SiAr ¹ Ar ² Ar ³ Substituted, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

wherein each R is ⁷ And R is ⁸ Independently an optionally further substituted 5-memberedOr a 6 membered aromatic or heteroaromatic ring;

wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, the compound has the structure of formula II:

wherein each R is ¹ 、R ² 、R ³ And R is ⁴ Independently hydrogen or a substituent selected from the group consisting of universal substituents as disclosed herein;

wherein any two adjacent substituents may be fused or joined to form a ring.

In another aspect, the present disclosure provides a formulation of a compound as described herein.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound as described herein.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound as described herein.

Drawings

Fig. 1 shows an organic light emitting device.

Fig. 2 shows an inverted organic light emitting device without a separate electron transport layer.

Detailed Description

A. Terminology

Unless otherwise specified, the following terms used herein are defined as follows:

As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and may be substantial in nature. In some cases, the small molecule may include a repeating unit. For example, the use of long chain alkyl groups as substituents does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core of a dendrimer, which consists of a series of chemical shells built on the core. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules" and all dendrimers currently used in the OLED field are considered small molecules.

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed" over "a second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed over" an anode even though various organic layers are present between the cathode and the anode.

As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.

A ligand may be referred to as "photosensitive" when it is believed that the ligand contributes directly to the photosensitive properties of the emissive material. When the ligand is considered not to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary", but the ancillary ligand may alter the properties of the photosensitive ligand.

As used herein, and as will be generally understood by those of skill in the art, if the first energy level is closer to the vacuum energy level, then the first "highest occupied molecular orbital" (Highest Occupied Molecular Orbital, HOMO) or "lowest unoccupied molecular orbital" (Lowest Unoccupied Molecular Orbital, LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level. Since Ionization Potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative). Similarly, a higher LUMO energy level corresponds to an Electron Affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with vacuum energy level on top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears closer to the top of this figure than the "lower" HOMO or LUMO energy level.

As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number relative to the vacuum level, this means that the "higher" work function is more negative (more negative). On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.

The terms "halo", "halogen" and "halo" are used interchangeably and refer to fluoro, chloro, bromo and iodo.

The term "acyl" refers to a substituted carbonyl (C (O) -R _s )。

The term "ester" refers to a substituted oxycarbonyl (-O-C (O) -R) _s or-C (O) -O-R _s ) A group.

The term "ether" means-OR _s A group.

The terms "thio" or "thioether" are used interchangeably and refer to-SR _s A group.

The term "seleno" refers to-SeR _s A group.

The term "sulfinyl" refers to-S (O) -R _s A group.

The term "sulfonyl" refers to-SO ₂ -R _s A group.

The term "phosphino" refers to-P (R _s ) ₂ A group wherein each R _s May be the same or different.

The term "silane group" means-Si (R _s ) ₃ A group wherein each R _s May be the same or different.

The term "germanium group" refers to-Ge (R) _s ) ₃ A group wherein each R _s May be the same or different。

The term "boron group" means-B (R _s ) ₂ A group or Lewis addition product-B (R) _s ) ₃ A group, wherein R is _s May be the same or different.

In each of the above, R _s May be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R _s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. In addition, alkyl groups may be optionally substituted.

The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, and the like. In addition, cycloalkyl groups may be optionally substituted.

The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. In addition, heteroalkyl or heterocycloalkyl groups may be optionally substituted.

The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl is essentially cycloalkyl including at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those containing from two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl, or heteroalkenyl groups may be optionally substituted.

The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Alkynyl is generally an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.

The term "aralkyl" or "arylalkyl" is used interchangeably and refers to an alkyl group substituted with an aryl group. In addition, aralkyl groups are optionally substituted.

The term "heterocyclyl" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Aromatic heterocyclic groups may be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers/sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.

The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.

The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-azaboron-1, 4-azaboron-nitrogen, boron-nitrogen-like compounds, and the like. In addition, heteroaryl groups may be optionally substituted.

Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective corresponding aza analogues, are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.

In many cases, the universal substituent is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, boron, and combinations thereof.

In some cases, preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some cases, more preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boron, aryl, heteroaryl, thio, and combinations thereof.

In other cases, the most preferred universal substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms "substituted" and "substituted" refer to substituents other than H bonded to the relevant position, such as carbon or nitrogen. For example, when R ¹ When single substitution is represented, then one R ¹ It must not be H (i.e., substitution). Similarly, when R ¹ Representing di-substitutionWhen then two R ¹ It must not be H. Similarly, when R ¹ R represents zero or no substitution ¹ For example, it may be hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or for ring atoms having a fully saturated valence, it may simply represent none, such as nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atom.

As used herein, "combination thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can contemplate from the applicable list. For example, alkyl and deuterium can combine to form a partially or fully deuterated alkyl group; halogen and alkyl may combine to form a haloalkyl substituent; and halogen, alkyl and aryl may combine to form a haloaralkyl. In one example, the term substitution includes a combination of two to four of the listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms other than hydrogen or deuterium, or combinations comprising up to forty atoms other than hydrogen or deuterium, or combinations comprising up to thirty atoms other than hydrogen or deuterium. In many cases, a preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.

The term "aza" in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic ring may be replaced with a nitrogen atom, for example and without limitation, aza-triphenylene encompasses dibenzo [ f, H ] quinoxaline and dibenzo [ f, H ] quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by those of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Yan Ming (Ming Yan) et al, tetrahedron 2015,71,1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Int. Ed.) (reviewed) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacement of aromatic ring hydrogen with deuterium, respectively.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linking fragments are considered equivalent.

In some cases, a pair of adjacent substituents may optionally be joined or fused into a ring. Preferred rings are five-, six-, or seven-membered carbocycles or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be next to each other on the same ring, or on two adjacent rings having two nearest available substitutable positions (e.g., the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene) so long as they can form a stable fused ring system.

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a compound of formula I:

wherein X is ¹ -X ⁸ Each independently is C or N;

Wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, the present disclosure provides a compound of formula II:

wherein R is ¹ 、R ² 、R ³ And R is ⁴ At least one of them is-L-SiAr ¹ Ar ² Ar ³ And R is ^A 、R ¹ 、R ² 、R ³ And R is ⁴ At least one of them is-NR ⁵ R ⁶ The method comprises the steps of carrying out a first treatment on the surface of the And wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, at least one of the following conditions is true:

1)X ¹ -X ⁸ at least one of which is N and R ^A At least one of which is a substituted biscarbazolyl group comprising silane;

wherein if L is aryl, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

wherein each R is ⁷ And R is ⁸ Independently is an optionally further substituted 5-or 6-membered aromatic or heteroaromatic ring;

wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, the compound is not

In some embodiments, Y ^A Is O or S and R ^A Carbazole that is not substituted with silyl-substituted carbazole.

In some embodiments, Y ^A Is not O or S, and R ^A Is a carbazole substituted with a silyl-substituted carbazole.

In some embodiments, the compound contains at least three carbazolyl groups.

In some embodiments, the compound contains exactly three carbazolyl groups.

In some embodiments, Y ^A Is NR and R ^A Not tertiary carbazole.

In some embodiments, Y ^A Is NR and R ^A Is a substituted or unsubstituted bicarbazole that is not substituted with another carbazole.

In some embodiments, Y ^A Is NR and R ^A Not 9'H-9,1':3',9 "-tertiary carbazole.

In some embodiments, each R, R', R ^A 、R ¹ 、R ² 、R ³ 、R ⁴ 、Ar ¹ 、Ar ² And Ar is a group ³ Independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some embodiments, wherein Ar ¹ 、Ar ² And Ar is a group ³ Each independently selected from the group consisting of: alkyl, cycloalkyl, heteroalkyl, aryl, heteroaryl, and combinations thereof, which may be further substituted.

In some embodiments, ar ¹ 、Ar ² And Ar is a group ³ At least one of which is an aryl group.

In some embodiments, ar ¹ 、Ar ² And Ar is a group ³ All of which are aryl groups.

In some embodiments, ar ¹ 、Ar ² And Ar is a group ³ Are all aryl groups which are not further substituted.

In some embodiments, Y ^A Is O.

In some embodiments, Y ^A Is S.

In some embodiments, Y ^A Is Se.

In some embodiments, Y ^A Is NR.

In some embodiments, Y ^A Is NR, wherein R in NR is a substituted or unsubstituted aryl or heteroaryl group.

In some embodiments, X ¹ -X ⁸ At least one of which is N and R ^A At least one of which is a substituted biscarbazolyl group comprising a silane.

In some embodiments, X ¹ -X ⁸ At least one of which is N and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein Si in the silane is directly attached to the dicarbazolyl moiety.

In some embodiments, X ¹ -X ⁸ At least one of which is N and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein Si in the silane is linked to the dicarbazolyl moiety via an organic linking group.

In some embodiments, X ¹ -X ⁸ At least one of which is N and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein the dicarbazole moiety is a 3,9 dicarbazole.

In some embodiments, X ¹ -X ⁸ At least one of which is N and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein the dicarbazole moiety is a 1,9 dicarbazole.

In some embodiments, Y ^A Is NR and R ^A At least one of them is a silane-containing warpSubstituted biscarbazolyl.

In some embodiments, Y ^A Is NR and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein Si in the silane is directly attached to the dicarbazolyl moiety.

In some embodiments, Y ^A Is NR and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein Si in the silane is linked to the dicarbazolyl moiety via an organic linking group.

In some embodiments, Y ^A Is NR and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein the dicarbazole moiety is a 3,9 dicarbazole.

In some embodiments, Y ^A Is NR and R ^A Is a substituted dicarbazolyl group comprising a silane, and wherein the dicarbazole moiety is a 1,9 dicarbazole.

In some embodiments, R ^A Is a carbazole moiety substituted with at least one group comprising silane and at least one substituted or unsubstituted carbazole.

In some embodiments, R ^A Is a carbazole moiety substituted with at least one group comprising a silane and at least one substituted or unsubstituted carbazole, and wherein Si in the silane is directly linked to the at least one substituted or unsubstituted carbazole.

In some embodiments, R ^A Is a carbazole moiety substituted with at least one group comprising a silane and at least one substituted or unsubstituted carbazole, and wherein Si in the silane is linked to the at least one substituted or unsubstituted carbazole via an organic linking group.

In some embodiments, R ^A Is a carbazole moiety substituted with at least one group comprising silane and at least one substituted or unsubstituted carbazole, and wherein the second carbazole moiety is substituted onto the first carbazole moiety at the 3-position.

In some embodiments, X ¹ -X ⁸ Each is C and X ¹ -X ⁴ At least one of the groups-L-SiAr ¹ Ar ² Ar ³ Substituted and X ¹ -X ⁸ At least one of the warp groups NR ⁵ R ⁶ Substitution; provided that if Y ^A Is O and X ⁴ Through SiPh ₃ Substituted, then X ⁵ -X ⁸ One of which is NR via said group ⁵ R ⁶ And (3) substitution.

In some embodiments, L is a direct bond.

In some embodiments, L is a substituted or unsubstituted aryl.

In some embodiments, L is substituted or unsubstituted heteroaryl.

In some embodiments, L is carbazolyl.

In some embodiments, R ⁵ And R is ⁶ Are all 6-membered aromatic or heteroaromatic rings.

In some embodiments, R ⁵ And R is ⁶ Are all 6-membered aromatic rings.

In some embodiments, R ⁵ And R is ⁶ To form a carbazolyl group.

In some embodiments, R ⁷ And R is ⁸ Are all 6-membered aromatic or heteroaromatic rings.

In some embodiments, R ⁷ And R is ⁸ Are all 6-membered aromatic rings.

In some embodiments, R ⁷ And R is ⁸ To form a carbazolyl group.

In some embodiments, R ^A One of them is NR ⁵ R ⁶ 。

In some embodiments, R ^A At least one of which is a silane-substituted biscarbazole.

In some embodiments, R ^A At least one of which is a silane-substituted biscarbazole, and wherein the silane group is a group-SiPh ₃ 。

In some embodiments, the compound comprises at least one dicarbazolyl group.

In one placeIn some embodiments, X ¹ via-SiAr ¹ Ar ² Ar ³ And (3) substitution.

In some embodiments, X ² via-SiAr ¹ Ar ² Ar ³ And (3) substitution.

In some embodiments, X ³ via-SiAr ¹ Ar ² Ar ³ And (3) substitution.

In some embodiments, X ⁴ via-SiAr ¹ Ar ² Ar ³ And (3) substitution.

In some embodiments, X ¹ Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, X ⁸ Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, X ² Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, X ⁷ Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, X ⁴ Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, X ⁵ Substituted with substituted or unsubstituted bicarbazoles.

In some embodiments, the compound comprises a substituted or unsubstituted bicarbazole.

In some embodiments, the substituted or unsubstituted bicarbazole is a 3,9 bicarbazole.

In some embodiments, the substituted or unsubstituted bicarbazole is a 1,9 bicarbazole.

In some embodiments, the substituted or unsubstituted bicarbazole is 4,9 bicarbazole.

In some embodiments, the compound is free of nitrile groups.

In some embodiments, the compound is selected from the group consisting of:

/>

wherein Y is ^B Selected from S and Se;

wherein T is ¹ To T ⁸ Each independently is C or N;

wherein T is ¹ To T ⁸ At least one of which is N;

wherein X is ¹ To X ²⁴ Each independently is C or N;

wherein L' is a substituted or unsubstituted aryl or heteroaryl group;

R ^B '、R ^C ' and R ^B To R ^I Each independently monosubstituted to the maximum allowable substitution or unsubstituted;

R ¹ 、R ^B '、R ^C ' and R ^B To R ^I Each independently is hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, L' is phenyl.

In some embodiments, L' is carbazole.

In some embodiments, the compound is selected from the group consisting of:

/>

where i is an integer from 1 to 144, j is an integer from 1 to 143, k is an integer from 1 to 15, and m, n and o are each independently an integer from 1 to 141, and,

Wherein Y1 to Y141 are NR1 to NR141, Y142 is S, Y143 is Se, and Y144 is O, and,

wherein R1 to R141 are defined in the following list:

/>

wherein C1 to C15 are defined in the following list:

/>

in some embodiments, the compound is selected from the group consisting of the compounds in the following list a:

/>

in some embodiments, a compound of formula I described herein may be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, deuterated percentages have their ordinary meaning and include the percentage of possible hydrogen atoms replaced by deuterium atoms (e.g., the position of hydrogen, deuterium, or halogen).

C. OLED and device of the present disclosure

In another aspect, the present disclosure also provides an OLED device comprising a first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

In some embodiments, the first organic layer may comprise a compound as disclosed herein.

In some embodiments, the compound may be a host, and the first organic layer may be an emissive layer comprising a phosphorescent or fluorescent emitter. Phosphorescence generally refers to photon emission with a change in electron spin, i.e., the initial and final states of the emission have different multiplicity, such as from the T1 to S0 state. Ir and Pt complexes currently widely used in OLEDs belong to the phosphorescent emitters. In some embodiments, such exciplex may also emit phosphorescence if exciplex formation involves triplet emitters. Fluorescent emitters, on the other hand, generally refer to photon emission with unchanged electron spin, such as from the S1 to S0 state. The fluorescent emitter may be a delayed fluorescent or non-delayed fluorescent emitter. Depending on the spin state, the fluorescent emitter may be a singlet emitter or a doublet emitter or other multiple state emitter. It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be increased by delaying fluorescence beyond the spin statistical limit of 25%. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. The P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA). On the other hand, the E-type delayed fluorescence does not depend on the collision of two triplet states, but on the thermal population between triplet and singlet excited states (thermal population). The thermal energy may activate a transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). The type E delayed fluorescence feature may be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that TADF requires a compound or exciplex having a small singlet-triplet energy gap (Δes-T) of less than or equal to 300, 250, 200, 150, 100, or 50 meV. There are two main types of TADF emitters, one is known as donor-acceptor TADF and the other is known as Multiple Resonance (MR) TADF. Typically, a donor-acceptor single compound is constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) and an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring). A donor-acceptor exciplex may be formed between the hole transporting compound and the electron transporting compound. Examples of MR-TADF include highly conjugated boron-containing compounds. In some embodiments, the reverse intersystem crossing (cross) time from T1 to S1 of the delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time may be greater than 10 microseconds and less than 100 microseconds.

In some embodiments, the compound is a host and the organic layer is an emissive layer comprising a phosphorescent material.

In some embodiments, the emissive dopant may be a phosphorescent or fluorescent material.

In some embodiments, the non-emissive dopant may also be a phosphorescent or fluorescent material.

In some embodiments, the OLED may comprise additional compounds selected from the group consisting of: fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material energy transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer, and the OLED further comprises an acceptor.

In some embodiments, the fluorescent material or delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the fluorescent material or delayed fluorescent material does not emit light within the OLED. In some embodiments, the fluorescent material or another material whose excited state is transferred into the OLED by delayed fluorescent material energy. In some embodiments, the fluorescent material or delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the fluorescent material or delayed fluorescent material is a sensitizer and the OLED further comprises an acceptor.

In some embodiments, the compound may be an acceptor, and the OLED may further comprise a sensitizer selected from the group consisting of delayed fluorescent materials, phosphorescent materials, and combinations thereof.

In some embodiments, the compound may be a fluorescent emitter, a delayed fluorescent material, or a component of an exciplex that is a fluorescent emitter or delayed fluorescent material.

In some embodiments, the compound is a host and the OLED comprises an acceptor as an emitter and a sensitizer selected from the group consisting of delayed fluorescent materials, phosphorescent materials, and combinations thereof; wherein the sensitizer transfers energy to the receptor.

In some embodiments, when the compound is a host, the compound may be an electron transporting host. In some of these embodiments, the compound has a LUMO below-2.4 eV. In some of these embodiments, the compound has a LUMO below-2.5 eV. In some of these embodiments, the compound has a LUMO below-2.6 eV. In some of these embodiments, the compound has a LUMO below-2.7 eV.

In some embodiments, the phosphorescent material may be a metal coordination complex having a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond. In some embodiments, the metal is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt. In some embodiments, the sensitizer compound has the formula M (L ¹ ) _x (L ² ) _y (L ³ ) _z ；

Wherein L is ¹ 、L ² And L ³ May be the same or different;

wherein x is 1, 2 or 3;

wherein y is 0, 1 or 2;

wherein z is 0, 1 or 2;

wherein x+y+z is the oxidation state of the metal M;

wherein L is ¹ Selected from the group consisting of the structures of the following ligand list:

/>

wherein L is ² And L ³ Independently selected fromAnd a group of structures of a list of ligands; wherein:

t is selected from the group consisting of B, al, ga and In;

K ¹ ' is a direct bond or is selected from NR _e 、PR _e O, S and Se;

each Y ¹ To Y ¹³ Independently selected from the group consisting of carbon and nitrogen;

y' is selected from the group consisting of: BR (BR) _e 、NR _e 、PR _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f ；

R _e And R is _f May be fused or joined to form a ring;

each R _a 、R _b 、R _c And R is _d May independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

each R _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c 、R _d 、R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of the universal substituents defined herein; and is also provided with

Wherein R is _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c And R is _d Any two of which may be fused or joined to form a ring or to form a multidentate ligand.

In some embodiments, formula M (L ¹ ) _x (L ² ) _y (L ³ ) _z The metal in (2) is selected from the group consisting of Cu, ag or Au.

In some embodiments of the OLED, the phosphorescent material has a formula selected from the group consisting of: ir (L) _A ) ₃ 、Ir(L _A )(L _B ) ₂ 、Ir(L _A ) ₂ (L _B )、Ir(L _A ) ₂ (L _C )、Ir(L _A )(L _B )(L _C ) And Pt (L) _A )(L _B )；

Wherein L is _A 、L _B And L _C In Ir compounds are different from each other;

wherein L is _A And L _B The Pt compounds may be the same or different; and is also provided with

Wherein L is _A And L _B In Pt compounds, tetradentate ligands can be formed by ligation.

In some embodiments, the phosphorescent material is selected from the group consisting of:

/>

wherein:

X ⁹⁶ to X ⁹⁹ Is independently C or N;

each Y ¹⁰⁰ Independently selected from the group consisting of NR ", O, S and Se;

l is independently selected from the group consisting of: direct key, BR'、BR”R”'、NR”、PR”、O、S、Se、C＝O、C＝S、C＝Se、C＝NR”、C＝CR”R”'、S＝O、SO ₂ CR ", CR" R ' ", siR" R ' ", ger" R ' ", alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

X ¹⁰⁰ at each occurrence selected from the group consisting of: o, S, se, NR "and CR" R' ";

each R ^10a 、R ^20a 、R ^30a 、R ^40a And R is ^50a 、R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E "and R ^F "independently means monosubstituted to maximum substitution, or unsubstituted;

R、R'、R”、R”'、R ^10a 、R ^11a 、R ^12a 、R ^13a 、R ^20a 、R ^30a 、R ^40a 、R ^50a 、R ⁶⁰ 、R ⁷⁰ 、R ⁹⁷ 、R ⁹⁸ 、R ⁹⁹ 、R ^A1 '、R ^A2 '、R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^G ”、R ^H ”、R ^I ”、R ^J ”、R ^K ”、R ^L ”、R ^M "and R ^N "each is independently hydrogen or a generic substituent as described herein; wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments of the OLED, the TADF emitter comprises at least one donor group and at least one acceptor group. In some embodiments, the TADF emitter is a metal complex. In some embodiments, the TADF emitter is a nonmetallic complex. In some embodiments, the TADF emitter is a Cu, ag, or Au complex.

In some embodiments of the OLED, the TADF emitter has the formula M (L ⁵ )(L ⁶ ) Wherein M is Cu, ag or Au, L ⁵ And L ⁶ Is different and L ⁵ And L ⁶ Independently selected from the group consisting of:

/>

wherein A is ¹ -A ⁹ Each independently selected from C or N;

wherein each R is ^P 、R ^P 、R ^U 、R ^SA 、R ^SB 、R ^RA 、R ^RB 、R ^RC 、R ^RD 、R ^RE And R is ^RF Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments of the OLED, the TADF emitter is selected from the group consisting of the structures in the following TADF list:

/>

in some embodiments of the OLED, the TADF emitter comprises at least one of the chemical moieties selected from the group consisting of:

wherein Y is ^T 、Y ^U 、Y ^V And Y ^W Each independently selected from the group consisting of: BR, NR, PR, O, S, se, C = O, S = O, SO ₂ BRR ', CRR', siRR ', and GeRR';

wherein each R is ^T May be the same or different, and each R ^T Independently is a donor, an acceptor group, an organic linking group bonded to the donor, an organic linking group bonded to the acceptor group, or an end group selected from the group consisting of: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, aryl, heteroaryl, and combinations thereof; and is also provided with

R and R' are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof.

In some of the above embodiments, any carbon ring atom up to a maximum of three in each benzene ring of any of the structures described above, along with its substituents, may be substituted with N.

In some embodiments, the TADF emitter comprises at least one chemical moiety selected from the group consisting of: nitriles, isonitriles, boranes, fluorides, pyridines, pyrimidines, pyrazines, triazines, aza-carbazole, aza-dibenzothiophenes, aza-dibenzofurans, aza-dibenzoselenophenes, aza-triphenylenes, imidazoles, pyrazoles, oxazoles, thiazoles, isoxazoles, isothiazoles, triazoles, thiadiazoles, and oxadiazoles.

In some embodiments, the fluorescent compound comprises at least one of the chemical moieties selected from the group consisting of:

/>

wherein Y is ^F 、Y ^G 、Y ^H And Y ^I Each independently selected from the group consisting of: BR, NR, PR, O, S, se, C = O, S = O, SO ₂ BRR ', CRR', siRR ', and GeRR';

wherein X is ^F And Y ^G Each independently selected from the group consisting of C and N; and is also provided with

Wherein R is ^F 、R ^G R, R and R' are each independently hydrogen or a substituent selected from the group consisting of the universal substituents defined herein.

In some embodiments of the OLED, the fluorescent compound is selected from the group consisting of:

/>

wherein Y is ^F1 To Y ^F4 Each independently selected from O, S and NR ^F1 ；

Wherein R is ^F1 And R is ^1S To R ^9S Each independently represents a single substitution to the maximum possible number of substitutions, or no substitution; and is also provided with

Wherein R is ^F1 And R is ^1S To R ^9S Each independently is hydrogen or a substituent selected from the group consisting of the universal substituents defined herein; wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, the emitter is selected from the group consisting of: />

/>

In some of the above embodiments, any carbon ring atom up to a maximum of three in each benzene ring of any of the structures described above, along with its substituents, may be substituted with N. In some embodiments, the compound may be an acceptor, and the OLED may further comprise a sensitizer selected from the group consisting of delayed fluorescent materials, phosphorescent materials, and combinations thereof.

In yet another aspect, the OLED of the present disclosure may further comprise an emissive region containing a compound as disclosed in the above compound section of the present disclosure. In some embodiments, the emissive layer further comprises an additional host, wherein the additional host comprises triphenylene comprising a benzo-fused thiophene or a benzo-fused furan;

wherein any substituents in the host are non-fused substituents independently selected from the group consisting of: c (C) _n H _2n+1 、OC _n H _2n+1 、OAr ₁ 、N(C _n H _2n+1 ) ₂ 、N(Ar ₁ )(Ar ₂ )、CH＝CH-C _n H _2n+1 、C≡CC _n H _2n+1 、Ar ₁ 、Ar ₁ -Ar ₂ 、C _n H _2n -Ar ₁ Or unsubstituted; wherein n is an integer from 1 to 10; and wherein Ar is ₁ And Ar is a group ₂ Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

In some embodiments, the additional body may be selected from the group consisting of:

/>

wherein:

X ¹ to X ²⁴ Is independently C or N;

l' is a direct bond or an organic linking group;

each Y ^A Independently selected from the group consisting of: no bond, O, S, se, CRR ', siRR', geRR ', NR, BR, BRR';

R ^A '、R ^B '、R ^C '、R ^D '、R ^E '、R ^F ' and R ^G Each of' independently represents mono-to maximum substitution or no substitution;

each R, R', R ^A '、R ^B '、R ^C '、R ^D '、R ^E '、R ^F ' and R ^G ' independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, boron, and combinations thereof; wherein any two adjacent substituents may be fused or joined to form a ring.

In some embodiments, the compound may be an acceptor, and the OLED may further comprise a sensitizer selected from the group consisting of delayed fluorescent emitters, phosphorescent emitters, and combinations thereof.

In some embodiments, the compound may be a fluorescent emitter, a delayed fluorescent emitter, or a component of an exciplex that is a fluorescent emitter or a delayed fluorescent emitter.

In yet another aspect, the OLED of the present disclosure may further comprise an emissive region containing a compound as disclosed in the above compound section of the present disclosure.

In some embodiments, the emissive region may comprise a compound as described herein.

In some embodiments, at least one of the anode, cathode, or new layer disposed on the organic emissive layer acts as an enhancement layer. The enhancement layer includes a plasma material exhibiting surface plasmon resonance that is non-radiatively coupled to the emitter material and transfers excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is provided at a threshold distance from the organic emissive layer that is no more than a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer, and the threshold distance is a distance where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emissive layer from the enhancement layer, but still allows energy to be outcoupled from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space in the form of photons. In other embodiments, the energy is scattered from the surface plasmon mode to other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered into the non-free space mode of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intermediaries may be disposed between the enhancement layer and the outcoupling layer. Examples of the interposer may be dielectric materials including organic, inorganic, perovskite, oxide, and may include stacks and/or mixtures of these materials.

The enhancement layer improves the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, improvement in emission linearity, variation in emission intensity and angle, variation in stability of the emitter material, variation in efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides can create an OLED device that utilizes any of the effects mentioned above. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, an OLED according to the present invention may also include any of the other functional layers that are typically found in an OLED.

The enhancement layer may be composed of a plasma material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasma material is a material whose real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasma material comprises at least one metal. In such embodiments, the metal may include at least one of the following: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. In general, metamaterials are media composed of different materials, wherein the media as a whole acts differently than the sum of its material components. Specifically, we define an optically active metamaterial as a material having both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media with dielectric constants or permeability having different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures (e.g., distributed bragg reflectors (Distributed Bragg Reflector, "DBRs")) because the medium should exhibit uniformity in the direction of propagation over the length scale of the wavelength of light. Using terminology that will be understood by those skilled in the art: the dielectric constant of a metamaterial in the direction of propagation can be approximately described by an effective medium. Plasma materials and metamaterials provide a means of controlling light propagation that can enhance OLED performance in a variety of ways.

In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodic, quasi-periodic, or randomly arranged wavelength-sizing features, or periodic, quasi-periodic, or randomly arranged sub-wavelength-sizing features. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

In some embodiments, the outcoupling layer has wavelength-sizing features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sizing features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outcoupling may be tuned by at least one of: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and/or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials and/or a core of one type of material, and which is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have an additional layer disposed thereon. In some embodiments, the polarization of the emission may be tuned using an outcoupling layer. Changing the dimensions and periodicity of the outcoupling layer may select a class of polarizations that preferentially outcouple to air. In some embodiments, the outcoupling layer also serves as an electrode of the device.

In yet another aspect, the present disclosure also provides a consumer product comprising an Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the disclosure.

In some embodiments, a consumer product comprises an Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as described herein.

In some embodiments, the consumer product may be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.

In general, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted when the exciton relaxes through a light emission mechanism. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

Several OLED materials and configurations are described in U.S. patent nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

Initial OLEDs used emissive molecules that emitted light ("fluorescence") from a singlet state, as disclosed, for example, in U.S. patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in time frames less than 10 nanoseconds.

Recently, OLEDs have been demonstrated that have emissive materials that emit light from a triplet state ("phosphorescence"). Baldo et al, "efficient phosphorescent emission from organic electroluminescent devices (Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices)", nature, vol.395, 151-154,1998 ("Baldo-I"); and Bardo et al, "Very efficient green organic light emitting device based on electrophosphorescence (Very high-efficiency green organic light-emitting devices based on electrophosphorescence)", applied physical fast report (appl. Phys. Lett.), vol.75, stages 3,4-6 (1999) ("Bardo-II"), incorporated by reference in its entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.

Fig. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers in sequence. The nature and function of these various layers and example materials are described in more detail in U.S. Pat. No. 7,279,704 at columns 6-10, which is incorporated by reference.

Further examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio ₄ m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0239980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety Incorporated in the manner used. Examples of cathodes are disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, that include composite cathodes having a thin layer of metal (e.g., mg: ag) containing an overlying transparent, electrically conductive, sputter-deposited ITO layer. The theory and use of barrier layers is described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implanted layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

Fig. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 may be fabricated by depositing the layers in sequence. Because the most common OLED configuration has a cathode disposed above an anode, and the device 200 has a cathode 215 disposed below an anode 230, the device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Fig. 2 provides one example of how some layers may be omitted from the structure of the apparatus 100.

The simple layered structure illustrated in fig. 1 and 2 is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Further, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to fig. 1 and 2.

Structures and materials not specifically described, such as OLEDs (PLEDs) comprising polymeric materials, such as disclosed in frank (Friend) et al, U.S. patent No. 5,247,190, which is incorporated by reference in its entirety, may also be used. By way of another example, an OLED with a single organic layer may be used. The OLEDs can be stacked, for example, as described in U.S. patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in fig. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Furster et al, and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Boolean et al, which are incorporated by reference in their entirety.

Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. Preferred methods for the organic layer include thermal evaporation, ink jet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Pat. No. 6,337,102, incorporated by reference in its entirety, furster et al), and deposition by organic vapor jet printing (OVJP, also known as Organic Vapor Jet Deposition (OVJD)), as described in U.S. Pat. No. 7,431,968, incorporated by reference in its entirety. Other suitable deposition methods include spin-coating and other solution-based processes. The solution-based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, the preferred method includes thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. patent nos. 6,294,398 and 6,468,819, incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and Organic Vapor Jet Printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit the particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, and 3 to 20 carbons are a preferred range. A material with an asymmetric structure may have better solution processibility than a material with a symmetric structure because an asymmetric material may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated according to embodiments of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from harmful substances exposed to the environment including moisture, vapors and/or gases, etc. The barrier layer may be deposited on the substrate, electrode, under or beside the substrate, electrode, or on any other portion of the device, including the edge. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. patent No. 7,968,146, PCT patent application No. PCT/US2007/023098, and PCT/US2009/042829, which are incorporated herein by reference in their entirety. To be considered as a "mixture", the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and/or simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of electronic component modules (or units), which may be incorporated into a wide variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc., that may be utilized by end user product manufacturers. The electronics assembly module may optionally include drive electronics and/or a power source. Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product that contains one or more light sources and/or one or more of some type of visual display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, tablet phones, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays (displays with a diagonal of less than 2 inches), 3-D displays, virtual or augmented reality displays, vehicles, video walls including a plurality of tiled displays, theatre or gym screens, phototherapy devices, and signs. Various control mechanisms may be used to control devices manufactured in accordance with the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18 ℃ to 30 ℃, and more preferably at room temperature (20-25 ℃), but can be used outside this temperature range (e.g., -40 ℃ to +80 ℃).

Further details regarding OLEDs and the definitions described above can be found in U.S. patent No. 7,279,704, which is incorporated herein by reference in its entirety.

The materials and structures described herein may be applied in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices such as organic transistors may employ the materials and structures.

In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, crimpable, collapsible, stretchable and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is an illumination panel.

In some embodiments, the compound may be an emissive dopant. In some embodiments, the compounds may produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as delayed fluorescence of type E, see, e.g., U.S. application No. 15/700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant may be a racemic mixture, or may be enriched in one enantiomer. In some embodiments, the compounds may be homoleptic (identical for each ligand). In some embodiments, the compounds may be compounded (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligands may all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand may be different from each other. This is also true in embodiments where the ligand coordinated to the metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate or hexadentate ligand. Thus, where the coordinating ligands are linked together, in some embodiments all of the ligands may be the same, and in some other embodiments at least one of the linking ligands may be different from the other ligand(s).

In some embodiments, the compound may be used as a component of an exciplex to be used as a sensitizer.

In some embodiments, the sensitizer is a single component, or one of the components, that forms an exciplex.

According to another aspect, a formulation comprising a compound described herein is also disclosed.

The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronics assembly modules, and lighting panels. The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, and the compound may be a non-emissive dopant in other embodiments.

In some embodiments, the emissive layer includes one or more quantum dots.

In yet another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may comprise one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or monovalent or multivalent variants thereof. In other words, the compounds of the invention or monovalent or multivalent variants thereof may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also known as supramolecules). As used herein, "monovalent variant of a compound" refers to the same moiety as the compound but with one hydrogen removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variant of a compound" refers to a moiety that is identical to the compound but where more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

D. Combinations of compounds of the present disclosure with other materials

Materials described herein as suitable for use in particular layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one of ordinary skill in the art may readily review the literature to identify other materials that may be used in combination.

a) Conductive dopants:

the charge transport layer may be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by the generation of charge carriers in the host material and, depending on the type of dopant, a change in Fermi level (Fermi level) of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.

b)HIL/HTL：

The hole injection/transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is generally used as a hole injection/transport material. Examples of materials include, but are not limited to: phthalocyanines or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, e.g. MoO _x The method comprises the steps of carrying out a first treatment on the surface of the p-type semiconducting organic compounds such as 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonitrile; a metal complex; a crosslinkable compound.

Examples of aromatic amine derivatives for the HIL or HTL include, but are not limited to, the following general structures:

Ar ¹ to Ar ⁹ Is selected from: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, naphthalene, anthracene, benzene, phenanthrene, fluorene, pyrene, and the like,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrole A benzodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, ar ¹ To Ar ⁹ Independently selected from the group consisting of:

wherein k is an integer of 1 to 20; x is X ¹⁰¹ To X ¹⁰⁸ Is C (including CH) or N; z is Z ¹⁰¹ Is NAr ¹ O or S; ar (Ar) ¹ Having the same groups as defined above.

Examples of metal complexes used in the HIL or HTL include, but are not limited to, the following general formula:

wherein Met is a metal that may have an atomic weight greater than 40; (Y) ¹⁰¹ -Y ¹⁰² ) Is a bidentate ligand, Y ¹⁰¹ And Y ¹⁰² Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a 2-phenylpyridine derivative. In another aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a carbene ligand. In another aspect, met is selected from Ir, pt, os, and Zn. In another aspect, the metal complex has a chemical structure as compared to an Fc ⁺ The minimum oxidation potential in solution of less than about 0.6V for Fc coupling.

Non-limiting examples of HIL and HTL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified with references disclosing those materials as follows: CN, DE, EP EP, JP07-, JP EP, EP JP07-, JP US, US US, WO US, US WO, WO.

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c)EBL：

An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking such a barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

d) A main body:

the light-emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria are met.

Examples of metal complexes used as hosts preferably have the general formula:

wherein Met is a metal; (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a bidentate ligand, Y ¹⁰³ And Y ¹⁰⁴ Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, the metal complex is:

wherein (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

In another aspect, met is selected from Ir and Pt. In another aspect, (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a carbene ligand.

In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; for example, the following aromatic compounds are usedHeterocyclic compounds are selected from the group consisting of: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains in the molecule at least one of the following groups:

wherein R is ¹⁰¹ Selected from the group consisting ofGroup of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition as Ar mentioned above. k is 0 to 20 or an integer of 1 to 20. X is X ¹⁰¹ To X ¹⁰⁸ Independently selected from C (including CH) or N. Z is Z ¹⁰¹ And Z ¹⁰² Independently selected from NR ¹⁰¹ O or S.

Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: US, WO WO, WO-based US, WO WO, US, US and US,

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e) Other emitters:

one or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is generally used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as type E delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN, EB, EP1239526, EP, JP, KR TW, US20010019782, US TW, US20010019782, US US, US US, WO US, US US, WO.

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f)HBL：

A Hole Blocking Layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking the barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, the compound used in the HBL contains the same molecules or the same functional groups as used in the host described above.

In another aspect, the compound used in the HBL contains in the molecule at least one of the following groups:

wherein k is an integer of 1 to 20; l (L) ¹⁰¹ Is another ligand, and k' is an integer of 1 to 3.

g)ETL：

An Electron Transport Layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

In one aspect, the compounds used in ETL contain in the molecule at least one of the following groups:

wherein R is ¹⁰¹ Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, when aryl or heteroaryl, have similar definitions as for Ar described above. Ar (Ar) ¹ To Ar ³ Has a similar definition to Ar mentioned above. k is an integer of 1 to 20. X is X ¹⁰¹ To X ¹⁰⁸ Selected from C (including CH) or N.

In another aspect, the metal complex used in ETL includes, but is not limited to, the following formula:

wherein (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atom O, N or N, N; l (L) ¹⁰¹ Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

Non-limiting examples of ETL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

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h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, CGL plays a fundamental role in performance, consisting of n-doped and p-doped layers for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrode. Electrons and holes consumed in the CGL are refilled with electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.

In any of the above mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any of the specifically listed substituents, such as but not limited to methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the present invention works are not intended to be limiting.

Experimental part:

synthesis of Compound H1

Step 1:

sodium tert-butoxide (10.96 g,114.0mmol,2.0 eq) was added to a suspension of 2-bromodibenzo [ b, d ] thiophene (15.0 g,57.0mmol,1.0 eq) and 9H-3,9' -dicarbazole (18.95 g,57.0mmol,1.0 eq) in dry toluene (150 mL) and the mixture was bubbled with nitrogen for 10 min. Allyl palladium (II) chloride dimer (1.043 g,2.850mmol,0.05 eq.) and di-tert-butyl (1, 1-diphenylprop-1-en-2-yl) phosphane (1.158 g,3.420mmol,0.06 eq.) were added with additional bubbling for 5 minutes. After heating at 100 ℃ for 22 hours, the reaction mixture was cooled to room temperature and slowly quenched with water (100 mL). After dilution with ethyl acetate (300 mL), the mixture was passed through a pad of celite (50 g) to break the suspension. The filtrate was transferred to a separatory funnel and the layers were separated. The organic layer was washed with saturated brine (50 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was adsorbed onto silica gel (80 g) and purified by column chromatography eluting with dichloromethane and hexane to give 9- (dibenzo [ b, d ] thiophen-2-yl) -9H-3,9' -biscarbazole (14.0 g,77% yield) as a white solid.

Step 2:

2.5M butyllithium (7.07 mL,17.7mmol,1.3 eq.) in hexane was added dropwise to a solution of 9- (dibenzo [ b, d ] thiophen-2-yl) -9H-3,9' -dicarbazole (7.0 g,13.6mmol,1.0 eq.) in anhydrous THF (125 mL) at-78deg.C and stirred for 20 min. The reaction mixture was warmed to 0 ℃, stirred for 1.5 hours, and then cooled to-78 ℃. A solution of chlorotrityl silane (4.4 g,15.0mmol,1.1 eq.) in anhydrous THF (20 mL) was added dropwise and the reaction mixture was slowly warmed to room temperature overnight. The reaction mixture was cooled to about 5 ℃ and diluted with saturated ammonium chloride (50 mL) and dichloromethane (300 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (2×200 mL). The combined organic layers were passed through a pad of silica gel (100 g) and a pad of celite (20 g), which was rinsed with dichloromethane (300 mL). The filtrate was concentrated to a volume of about 50mL under reduced pressure and partitioned with hexane (300 mL). The mixture was recrystallized at room temperature overnight, filtered and washed with hexane (100 mL) to give compound H1 (9.6 g,91% yield) as an off-white solid.

Synthesis of Compound H2

A suspension of 6- (triphenylsilyl) -9H-3,9' -biscarbazole (6.499 g,11.00mmol,1.0 eq), 3-iodo-9-phenyl-9H-carbazole (4.467 g,12.10mmol,1.1 eq) and potassium phosphate (4.670 g,22.00mmol,2.0 eq) in anhydrous DMSO (60 mL) was bubbled with nitrogen for 10 min. Picolinic acid (0.677 g,5.50mmol,0.5 eq.) and copper (I) iodide (419.0 mg,2.20mmol,0.2 eq.) were added with additional bubbling for 5 minutes. After heating at 106 ℃ for 3 hours, the reaction mixture was cooled to room temperature and diluted with water (100 mL). The resulting solid was filtered and washed with water (50 mL). The solid was dissolved in dichloromethane (200 mL), loaded onto silica gel (120 g) and purified by column chromatography eluting with dichloromethane and hexane to give compound H2 (6 g,66% yield) as a white solid.

Synthesis of Compound H3

Step 1

To a 1L flask was added 1-fluoro-3-methoxy-2-nitrobenzene compound H3-1 (62.33 g,1 equivalent, 364.2 mmol), 2-bromophenylthiol compound H3-2 (72.31 g,1.05 equivalent, 382.4 mmol) and DMF (600.0 mL) to give a clear solution. Cs is then added ₂ CO ₃ (237.3 g,2 equivalents, 728.5 mmol). The reaction mixture was vigorously stirred at 100℃for 20h. The reaction mixture was slowly poured into 4L of ice water. The yellow suspension was stirred briefly, filtered, rinsed sequentially with 1L water and 400mL methanol, and dried in air overnight. Compound H3-3 was obtained as a fine pale yellow solid (81.1 g, yield 69.6%).

Step 2

To a 1L flask equipped with a reflux column and a stirring bar was added (2-bromophenyl) (3-methoxy-2-nitrophenyl) sulfide compound H3-3 (81.00 g,1 eq, 238.1 mmol), ethanol (262.5 mL), water (61.25 mL), concentrated HCl (3.5 mL) and iron (133.0 g,10 eq, 2.381 mol) and stirred at 75℃for 3H. The mixture was filtered through a pad of celite and rinsed with hot ethanol. The filtrate was concentrated to give compound H3-4 as a light brown solid (67 g, yield 91%).

Step 3

To a 2L flask was added 2- ((2-bromophenyl) thio) -6-methoxyaniline compound H3-4 (67.00 g,1 eq, 216.0 mmol), acetic acid (500.0 mL), acetonitrile (500.0 mL) and stirred at 0 ℃ (ice bath) for 30min. Tert-butyl nitrite (33.41 g,38.6mL,1.5 eq, 324.0 mmol) was added dropwise over 30min. The dark red solution was stirred for 60min. The ice bath was removed and the reaction solution was warmed to room temperature and then heated to 80 ℃. N is observed ₂ Is provided. The reaction was stirred at 80 ℃ overnight. Cooling to room temperature under vacuumConcentrated to give a red residue. The residue was purified by column chromatography eluting with DCM and heptane, then concentrated to dryness, wet triturated with hexane (150 mL) to give compound H3-5 as a white solid (33 g, 52% yield).

Step 4

Preparation of 6-bromo-1-methoxydibenzo [ b, d ] in a 1L flask equipped with a stirring bar]A suspension of thiophene H3-5 (18.30 g,1 eq, 62.42 mmol), diethyl ether (330.000 mL) was stirred briefly under nitrogen. Connecting new N ₂ An air bag. The reaction mixture was then cooled to-30 ℃ to give a white suspension. N-butyllithium (4.798 g,46.81mL,1.6M in hexane, 1.2 eq., 74.90 mmol) was added dropwise over 20 min. It was stirred at-30 ℃ to-10 ℃ for 2.5h and then cooled to-78 ℃ (dry ice acetone bath). Dichlorodiphenylsilane (16.59 g,1.05 eq, 65.54 mmol) was added over 2 min. The reaction was stirred at-78 ℃ for 20min, slowly warmed to room temperature (about 1.5 h) and kept stirring for 1h. The reaction mixture was cooled again to-78 ℃. Phenyl lithium (7.869 g,49.28mL,1.9 moles, 1.5 equivalents, 93.63 mmol) was added dropwise over 5 min. The reaction mixture was slowly warmed to room temperature overnight. 300mL of water was slowly added to quench the reaction. 300mL of EtOAc was then added and the two phases were separated. The aqueous phase was extracted with EtOAc (300 mL). The combined organics were washed with 80mL brine, briefly with MgSO ₄ Dried, filtered and concentrated in vacuo to give a yellow residue. This crude residue was combined with another batch prepared in the same manner, then vigorously stirred in 7.5% DCM in hexane for 2h, filtered, and then dried in air. Compound H3-6 was obtained as a white solid (40.5 g, 84% yield).

Step 5

To be equipped with stirring170ml DCM was added to a 250ml flask of the stick and the mixture was poured into N ₂ Stirring in ice water bath for 5min. Pure BBr was added drop wise during a period of 10min ₃ (42.4 g,169 mmol) and stirred briefly at room temperature. To a 1L flask equipped with an addition funnel and stirring bar was added (9-methoxydibenzo [ b, d)]Thiophen-4-yl) triphenylsilane compound H3-6 (40.05 g,1 eq, 84.73 mmol) and DCM (600.00 mL). The solution was stirred in an ice bath for 15min. Then, the above BBr ₃ The solution was transferred via cannula to the addition funnel and then added dropwise over a period of 55 min. The reaction mixture was stirred cold for 30min and then slowly warmed to 15 ℃ over 3 h. Slowly add 1L saturated NaHCO ₃ . The aqueous layer was extracted with 1L DCM. The organics were concentrated in vacuo to give compound H3-7 (39.8 g) as a white solid which was used in the next step without further purification.

Step 6

To a 1L flask equipped with an addition funnel and stirring bar was added 6- (triphenylsilyl) dibenzo [ b, d ]]Thiophen-1-ol Compound H3-7 (38.60 g,1 eq, 84.16 mmol) and DCM (600.0 mL) and under N ₂ Stirring in ice-water bath. Triethylamine (13.63 g,18.8mL,1.6 eq, 134.7 mmol) was added over 10min to give a clear solution. Trifluoromethanesulfonic anhydride (28.49 g,16.95mL,1.2 eq, 101.0 mmol) was added dropwise over 35min and stirred in an ice water bath for 1h. 300mL of water was added. The aqueous phase was extracted with DCM (300 mL). The combined organics were treated with MgSO ₄ Briefly dried, filtered and concentrated to give a pale yellow residue. Purification by column chromatography eluting with DCM and heptane afforded compound H3-8 as a white solid, 32.6g (65% yield in 2 steps).

Step 7

To a 250mL circle equipped with a baffle and stirring barThe bottom flask was charged with 6- (triphenylsilyl) dibenzo [ b, d]Thiophen-1-yl trifluoromethanesulfonate Compound H3-8 (22.30 g,1 equivalent, 37.75 mmol), xylene (350 mL), and use N ₂ Bubbling for 30min. Tert-butyl carbamate (11.06 g,2.5 eq, 94.38 mmol), 2-dicyclohexylphosphine-2, 6-dimethoxy-1, 1-biphenyl (2.325 g,0.15 eq, 5.663 mmol), pd were added together ₂ (dba) ₃ (2.593 g,0.075 eq., 2.831 mmol), K ₃ PO ₄ (24.04 g,3 equivalents, 113.3 mmol). By N ₂ The headspace of the flask was flushed for 10min. Connecting new N ₂ An air bag. The reaction mixture was stirred at 100℃for 3h. The reaction mixture was cooled to room temperature, filtered through celite pad, rinsed with EtOAc (3×60 mL), and concentrated to give compound H3-9 (33 g) as a red solid, which was used in the next step without further purification.

Step 8

To a 500ml flask equipped with a stirring bar and a septum was added (6- (triphenylsilyl) dibenzo [ b, d)]T-butyl thiophen-1-yl) carbamate compound H3-9 (33 g), DCM (210.00 mL) and stirred briefly in an ice bath. 2, 2-trifluoroacetic acid (43.04 g,28.9mL,10 equivalents, 377.5 mmol) was then added dropwise over 30min to give a dark solution. The ice bath is removed. The solution was stirred at room temperature for 3h. The reaction mixture was cooled and stirred briefly in an ice bath. Slowly adding saturated NaHCO ₃ Aqueous (about 350 mL) until a pH of about 8. The aqueous phase was extracted with DCM (400 mL). The combined organics were treated with MgSO ₄ Briefly dried, filtered and concentrated. The residue was combined with a sample from another batch of the same reaction and purified by column chromatography eluting with DCM and heptane to give compound H3-10 as a yellow solid, 20.3g (combined yield of 2 steps 88%).

Step 9

To a 500mL round bottom flask equipped with a septum and a stirring bar was added Compound H3-12 (9.250 g,0.8 eq, 46.06 mmol), compound H3-11 (17.32 g,1 eq, 57.57 mmol), dioxane (175.00 mL), water (35.000 mL), na ₂ CO ₃ (15.26 g,2.5 equivalents, 143.9 mmol). By N ₂ The mixture was bubbled for 40min. Tetrakis (triphenylphosphine) palladium (0) (1.996 g,0.03 eq, 1.727 mmol) was added. By N ₂ The headspace of the flask was flushed for 10min. Connecting new N ₂ An air bag. The reaction mixture was stirred at 90℃for 16h. The reaction mixture was cooled to room temperature. Water (100 mL) and EtOAc (100 mL) were added. The aqueous layer was extracted again with EtOAc (150 mL). The combined organics were treated with MgSO ₄ Briefly dried, filtered and concentrated. The residue was purified by column chromatography eluting with heptane to give compound H3-13 (11.28 g, yield 75%) as a transparent oil.

Step 10

To a 1-L flask, 2 '-dibromo-5-fluoro-1, 1' -biphenyl compound H3-13 (11.20 g,1.0 eq, 33.94 mmol), 9H-carbazole (6.243 g,1.1 eq, 37.33 mmol) and DMF (80.00 mL) were added to give a clear solution. Cs is then added ₂ CO ₃ (33.18 g,3 equivalents, 101.8 mmol). The reaction mixture was vigorously stirred at 120℃for 20h. The reaction mixture was cooled to room temperature and slowly poured into 400mL of ice water. EtOAc (250 mL) was added. The aqueous layer was again extracted with EtOAc (250 mL). The combined organics were treated with MgSO ₄ Briefly dried, filtered and concentrated. The residue was purified by column chromatography eluting with DCM and heptane to give compound H3-14 as a white solid, 8.6g (yield 54%).

Step 11

To a 500mL circle equipped with a baffle and stirring barThe bottom flask was charged with 6- (triphenylsilyl) dibenzo [ b, d]Thiophene-1-amine (to give Compound H3-10 (7.000 g,1 equivalent, 15.29 mmol)), 9- (2, 2 '-dibromo- [1,1' -biphenyl)]-4-yl) -9H-carbazole (giving compound H3-14 (7.299 g,1 eq, 15.29 mmol)), xylene (300 mL), and with N ₂ Bubbling for 30min. Dicyclohexylphosphine-2, 6-dimethoxy-1, 1-biphenyl (1.256 g,0.2 eq., 3.059 mmol), pd were added in one portion ₂ (dba) ₃ (1.401 g,0.1 eq., 1.529 mmol), K ₃ PO ₄ (9.739 g,3 eq, 45.88 mmol). By N ₂ The headspace of the flask was flushed for 10min. Connecting new N ₂ An air bag. The reaction mixture was stirred at 130℃for 20h. The reaction mixture was cooled to room temperature, filtered through a pad of celite, rinsed with EtOAc (3×200 mL) and concentrated. The residue was combined with a sample from another batch of the same reaction and purified by column chromatography eluting with DCM and heptane to give 13.7g of compound H3 as a solid.

Synthesis of Compound H4

Step 1:

To a 500mL round bottom flask was added 1-bromo-4-chlorodibenzo [ b, d ] furan (5.000 g,1 eq, 17.76 mmol) and the flask was flushed with nitrogen for 5 minutes. Anhydrous THF (100.00 mL) was added under nitrogen and the solution was cooled to-78 ℃. N-butyllithium (1.707 g,10.66ml,2.5 moles, 1.5 equivalents, 26.64 mmol) was added dropwise and stirred at-78 ℃ for one hour. Trichloro (phenyl) silane (4.508 g,3.413ml,1.2 eq, 21.31 mmol) was then added dropwise and the solution was allowed to warm to room temperature over one hour and stirred further at room temperature for four hours. The reaction mixture was cooled again to-78 ℃, then phenyl lithium (5.971 g,37.39ml,1.9 moles, 4 equivalents, 71.04 mmol) was added dropwise over ten minutes and allowed to warm to room temperature overnight. Water (80 mL) and ethyl acetate (80 mL) were added and the mixture was transferred to a separatory funnel. The organics and aqueous layer were separated and the aqueous layer was extracted twice with ethyl acetate (50 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography eluting with DCM and heptane. Pure fractions were combined and concentrated under reduced pressure to give compound H4-1 (2.5 g, yield 30%) as a white solid.

Step 2:

pd was added to a 250ml round bottom flask ₂ (dba) ₃ (0.2384 g,0.05001 equivalent, 260.3. Mu. Mol), (4-chlorodibenzo [ b, d)]Furan-1-yl) triphenylsilane Compound H4-1 (2.400 g,1 eq, 5.206 mmol), 9H-3,9' -Bicarbazol (2.250 g,1.3 eq, 6.767 mmol), di-tert-butyl (2 ',4',6' -triisopropyl- [1,1' -biphenyl)]-2-yl) phosphane (221.1 mg,0.1 eq, 520.6. Mu. Mol), sodium 2-methylpropane-2-carboxylate (1.501 g,3 eq, 15.62 mmol) and xylene (50.00 mL). The reaction mixture was bubbled with nitrogen for 15 minutes and then stirred at 135 ℃ overnight. After cooling the reaction to room temperature, water (50 mL) was added and the mixture was transferred to a separatory funnel. The organics and aqueous layer were separated and the aqueous layer was extracted twice with ethyl acetate (50 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography eluting with ethyl acetate and heptane. Pure fractions were combined and concentrated under reduced pressure to obtain compound H4 (2 g, yield 50%) as a white solid.

Synthesis of Compound H5

Step 1

(8-bromodibenzo [ b, d ] furan-2-yl) triphenylsilane to a dry 250mL flask was added 2, 8-dibromodibenzo [ b, d ] furan (10.00 g,1 equivalent, 30.68 mmol) and THF (153 mL) under nitrogen. The solution was cooled to-60 ℃. Lithium hexyl (13.34 ml,2.3 moles, 1.0 eq, 30.68 mmol) in hexane was added dropwise over 5 minutes and the solution stirred at-60 ℃ for 1 hour. Chlorotrityl silane (10.85 g,1.2 eq, 36.81 mmol) was added as a suspension to THF (60 mL). When the reaction mixture was warmed to room temperature, it was stirred overnight. The reaction mixture was quenched by the addition of methanol (15 mL) and diluted with dichloromethane (150 mL). The organic layer was washed once with water and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The resulting yellow oil was purified by silica gel vacuum chromatography for elution of 0-5% DCM in heptane to give (8-bromodibenzo [ b, d ] furan-2-yl) triphenylsilane (8.00 g,15.8mmol, 51.6%).

Step 2

9- (8- (triphenylsilyl) dibenzo [ b, d ] furan-2-yl) -9H-3,9 '-biscarbazole A3-necked flask was charged with 9H-3,9' -biscarbazole (7.891 g,1.5 eq., 23.74 mmol), (8-bromodibenzo [ b, d ] furan-2-yl) triphenylsilane (8.000 g,1 eq., 15.83 mmol), potassium phosphate (10.08 g,3.0 eq., 47.48 mmol), copper (I) iodide (3.014 g,1 eq., 15.83 mmol) and toluene (158 mL). The reaction mixture was heated to reflux for 36 hours. The reaction mixture was filtered through celite plug and rinsed with DCM (300 mL). The filtrate was concentrated to give a viscous brown solid. The brown solid was wet triturated in 1:3 DCM/methanol and the solid was collected via vacuum filtration to give Compound H5 (7.950 g,10.50mmol, 66.36%).

Synthesis of Compound H6

Step 1: to a 500mL flask was added 8-bromo-1-chlorodibenzo [ b, d ] furan (20.00 g,1 eq, 71.04 mmol) and THF (284 mL) under nitrogen. The solution was cooled to-78 ℃ and n-hexyllithium (35.5 ml,2.30 moles, 1.15 equivalents, 81.7 mmol) was slowly added to the hexane and the mixture was stirred at-78 ℃ for two hours. A solution of chlorotrityl silane (31.4 g,1.5 eq, 107 mmol) in THF (70 mL) was then slowly added. The mixture was allowed to stir overnight as it slowly warmed to room temperature. Water (200 mL) was added to the reaction mixture. The organic layer was separated and the aqueous layer was extracted with EtOAc (2×200 mL). The combined organic layers were washed with brine (300 mL), dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated dark yellow solution was allowed to stand overnight, which resulted in a white crystalline bag (pocket). Stirring was performed, after which time period of rest, further white powder was produced, the semi-solid material was broken up with a spatula and filtered under vacuum, after which washing with n-heptane to give (9-chlorodibenzo [ b, d ] furan-2-yl) triphenylsilane (15.17 g,43% yield).

Step 2: to a 500mL flask was added xylene (134 mL), sodium t-butoxide (8.03 g,2.73 equivalents, 83.55 mmol), 9H-3,9' -dicarbazole (10.17 g,1 equivalents, 30.61 mmol), and (9-chlorodibenzo [ b, d ] furan-2-yl) triphenylsilane (14.11 g,1 equivalents, 30.61 mmol) under nitrogen. The mixture was heated to reflux and then a solution of bis (tri-t-butylphosphine) palladium (0) (782.1 mg,0.05 eq, 1.530 mmol) in xylene (5 mL) was added quickly. After heating at reflux overnight, the reaction was cooled to room temperature. The reaction mixture was washed with water (2X 100 mL) and brine (150 mL). The organic layer was concentrated to give a dark brown oil which solidified upon standing overnight to give compound H6. The crude solid was further purified to give a pure white solid (1.7 g,7.3% yield).

Synthesis of Compound H7

Step 1: to a 3L flask were added potassium phosphate (38.31 g,3 equivalents, 180.5 mmol), 9H-3,9' -dicarbazole (20.00 g,1 equivalents, 60.17 mmol), 3, 6-dibromo-9-phenyl-9H-carbazole (50.68 g,2.1 equivalents, 126.3 mmol), toluene (602 mL), cyclohexane-1, 2-diamine (13.74 g,14mL,2 equivalents, 120.3 mmol), and copper (I) iodide (11.46 g,1 equivalents, 60.17 mmol). The solution was heated to reflux for 24h. The reaction mixture was cooled to room temperature and filtered through a plug of silica gel and basic alumina (eluting with dichloromethane). The filtrate was concentrated onto celite and column chromatography was performed on a silica gel column (960 g) eluted with heptane: DCM. The fractions containing the pure product as determined by TLC analysis were combined and concentrated to give 6-bromo-9-phenyl-9H-3, 9':3',9 "-tert-carbazole (13.0 g; 33%).

Step 2: to the flask was added 6-bromo-9-phenyl-9H-3, 9':3',9 "-tert-carbazole (13.0 g,1 eq, 19.9 mmol) and THF (100 mL) under nitrogen and the solution was cooled to-78 ℃. Lithium hexyl solution (12.0 ml,2.3m,1.39 eq, 27.6 mmol) in hexanes was added dropwise and the reaction stirred for 1h. Chlorotrityl silane (10.2 g,1.74 eq, 34.7 mmol) in THF (5 mL) was then added slowly. The reaction was warmed to room temperature and stirred for 48h. The reaction was treated with saturated NH ₄ The aqueous Cl solution was quenched and extracted with ethyl acetate. The combined organic layers were taken up over Na ₂ SO ₄ Dried, filtered and concentrated. The resulting thick blue oil was passed through a plug of silica gel and basic alumina (eluting with dichloromethane). The filtrate was concentrated to give a colorless solid. The solid was dissolved in dichloromethane (60 mL) and poured into stirring methanol (650 mL). The resulting solid was collected via suction filtration. The solid was then dissolved in ethyl acetate (150 mL) and poured into methanol (1.8L). The solids were collected via suction filtration. The solid was adsorbed onto celite and subjected to column chromatography on silica gel (560 g) eluting with methylene chloride (0-28%) in heptane. The fractions containing the pure product analyzed by TLC were combined and concentrated to give 9-phenyl-6- (triphenylsilyl) -9H-3,9':3',9 "-tert-carbazole (15.23 g; 78%) as a white solid.

Synthesis of compound H8:

step 1:

into a 2L flask was charged 2, 8-dibromodibenzo [ b, d ]]Thiophene (21.61 g,3.5 eq, 63.17 mmol), 9H-3,9' -dicarbazole (6.000 g,1.0 eq, 18.05 mmol), tripotassium phosphate (11.49 g,3 eq, 54.15 mmol) and toluene (250 mL), and the resulting mixture was treated with N ₂ Bubbling for 20min. Although stillCopper (I) iodide (3.438 g,1 eq, 18.05 mmol) and cyclohexane-1, 2-diamine (2.061 g,1 eq, 18.05 mmol) were bubbled through. The bubbling was stopped and the mixture was heated to reflux. After 3 days, the reaction was incomplete. The mixture was cooled to ambient temperature and a second portion of cyclohexane-1, 2-diamine (2.061 g,1 eq., 18.05 mmol) and copper (I) iodide (3.438 g,1 eq., 18.05 mmol) were added with bubbling. The reaction mixture was poured warm through a celite plug. The filter cake was washed with warm toluene (100 mL). The filtrate was washed with water (2×300 mL) and the organic layer was concentrated to a solid. The reaction material was loaded onto celite and chromatographed on silica gel (eluting with 0-30% DMC in heptane). The purest fractions were combined and concentrated to give 9- (8-bromodibenzo [ b, d)]Thiophen-2-yl) -9H-3,9' -biscarbazole (6.100 g,10.28mmol, 57%).

Step 2:

the flask was charged with 9- (8-bromodibenzo [ b, d)]Thiophen-2-yl) -9H-3,9' -biscarbazole (2.00 g,1 eq, 3.37 mmol) and THF (60 mL) and the mixture was cooled to-78 ℃. A solution of hexyllithium (1.47 mL,2.3M,1 eq., 3.37 mmol) was added dropwise, maintaining the temperature below-55deg.C. The reaction was stirred cold for 1h. A solution of dimethoxydiphenylsilane (0.800 mL,1.05 eq, 3.54 mmol) in THF (30 mL) was added. The reaction mixture was allowed to slowly warm to ambient temperature overnight. The reactants are treated by adding saturated NH ₄ Aqueous Cl (15 mL) was quenched. The organic layer was separated and concentrated under reduced pressure. The residue was chromatographed on silica gel (eluting with 30% DCM in heptane). The fractions containing the product were combined and concentrated to dryness to give 9- (8- (methoxydiphenylsilyl) dibenzo [ b, d)]Thiophen-2-yl) -9H-3,9' -dicarbazole (2.5 g). Assuming quantitative yield, the product was used as is in the next step.

Step 3:

the flask was charged with bromobenzene (1.063 g,1.2 eq, 6.768 mmol) and THF (30 mL). The resulting solution was cooled to-78 ℃ and butyllithium (2.94 ml,2.3m,1.2 eq., 6.77 mmol) was added dropwise. The reaction was stirred cold for 1h. Addition of 9- (8- (methoxydiphenylsilyl) dibenzo [ b, d) ]A solution of thiophen-2-yl) -9H-3,9' -biscarbazole (4.100 g,1 eq, 5.640 mmol) in THF (30 mL). The reaction mixture was allowed to slowly warm to ambient temperature overnight. Addition of saturated NH to the reaction mixture ₄ Aqueous Cl (3 mL) and 12g of celite. The mixture was concentrated to dryness. The residue was chromatographed on silica gel (eluting with 0-30% DCM in heptane). The fractions containing the desired product were combined and concentrated to give 9- (8- (triphenylsilyl) dibenzo [ b, d) as a white solid]Thiophen-2-yl) -9H-3,9' -biscarbazole compound H8 (4.100 g,5.304mmol, 94.04%).

OLED devices were fabricated using compound H1, compound H2, compound H5, compound H6, compound H7, and compound H9 as hole-transporting hosts. The device results are shown in Table 1, where EQE and voltage are at 10mA/cm ² Lower acquisition, and lifetime (LT ₉₀ ) Is at 20mA/cm ² The time for which the luminance was reduced to 90% of the initial luminance at the constant current density of (c).

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The OLED was grown on a glass substrate pre-coated with an Indium Tin Oxide (ITO) layer having a sheet resistance of 15- Ω/sq. The substrate is degreased with a solvent prior to any organic layer deposition or coating, and then treated with oxygen, etc. at 100 millitorr and 50W The plasma was treated for 1.5 minutes and with UV ozone for 5 minutes. At high vacuum<10 ^-6 Tray) is manufactured by thermal evaporation. The anode electrode isIndium Tin Oxide (ITO). All devices were placed in a nitrogen glove box (H) ₂ O and O ₂ <1 ppm) is sealed with an epoxy-sealed glass lid and the desiccant is incorporated into the package. The doping percentages are in volume percent.

The device shown in table 1 has an organic layer consisting of, in order: starting from the surface of the ITO,compound 1 (HIL), of (E)>Compound 2 (HTL), of (a)>Compound 3 (EBL),>40% compound 4 and 12% emitter 1 doped HHost (EML), -, for example>Compound 4 (BL),>35% of compound 6 doped compound 5 (ETL),/o>Compound 5 (EIL) of (2), followed by +.>Al (cathode). The case of HHost for each example is shown in table 1. Example of value reporting device with respect to comparative example 1LT of 1-5 ₉₀ 。

Table 1: device data

The above data shows that device examples 1-5 each exhibit a longer lifetime than the comparative device using comparative compound H9. The 22-110% longer lifetime exceeded any value attributable to experimental error, and the observed improvement was significant. A large life gain is achieved with less than 5% change in EQE and V. The compounds of the present invention have a similar structure to the comparative compounds, differing only in the selection of DBF, DBT and carbazole and the substitution patterns of the dicarbazole and triphenylsilane groups. The significant performance improvements observed in the above data are unexpected based on the fact that the compounds have similar structures and similar optoelectronic properties as shown in table 2. In particular, compound H1, which is a DBT analog of compound H9, exhibits a 22% enhancement in lifetime despite having the same biscarbazole and triphenylsilane substitution patterns. Similarly, compound H5 and compound H6 are isomers of compound H8 and each have a longer lifetime of more than 100%. Together, these results indicate that the location of the selection and substitution of the fused ring moieties are important for the lifetime of the device. Without being bound by any theory, this improvement may be attributed to the removal of the undesired reaction path between DBF and triphenylsilane when the silane group is substituted in the ortho position to the oxygen atom.

Table 2: optoelectronic data

	T1(nm)	HOMO(eV)	LUMO(eV)
				Compound H1	412	-5.53	-2.13
Compound H2	408	-5.51	-1.91
				Compound H3	410	-5.57	-2.1
Compound H4	417	-5.57	-2.19
				Compound H5	406	-5.53	-2.06
Compound H6	408	-5.54	-2.02
				Compound H7	409	-5.5	-1.88
Compound H9	409	-5.53	-2.12

T1 of the above compound was obtained from the short wavelength onset (20% of peak maximum) of the gated emission of the frozen sample in 2-MeTHF at 77K. Gated emission spectra were collected on a Horiba Fluorolog-3 spectrofluorimeter, equipped with a xenon flash lamp with a flash delay of 10 ms and a collection window of 50 ms. All samples were excited at 300 nm.

The HOMO and LUMO values of the above samples were determined electrochemically using solutions. Solution cyclic voltammetry and differential pulse voltammetry were performed using a CH instrument model 6201B potentiostat and using anhydrous dimethylformamide solvent and tetrabutylammonium hexafluorophosphate as supporting electrolytes. The glassy carbon and platinum and silver wires were used as working, counter and reference electrodes, respectively. Electrochemical potential reference internal ferrocenium-ferrocenium redox couple (Fc/Fc) by measuring peak potential difference from differential pulse voltammetry ⁺ ). According to the literature, the respective Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energies ((a) feng (Fink), r.; heskel (Heischkel), y.; selakkat (Thelakkat), m.; schmidt (Schmidt), h.—w. material chemistry (chem. Mater.) 1998,10,3620-3625 (b) bomer (Pommerehne), j.; westerweber (vesdweber), h.; gas (Guss), w.; macht (Mahrt), r.f.; basler, h.; porsch), m.; dobby (Daub), advanced material (j. Adv. Mater.) 1995,7,551 are determined by reference to the cation and anion redox potentials of ferrocene (4.8 eV versus vacuum).

Claims

1. A compound of the formula I,

wherein X is ¹ -X ⁸ Each independently is C or N;

wherein Y is ^A Selected from the group consisting of: o, S, se; NR, BR, BRR', PR, CR, c=o,

C＝NR、C＝CRR'、C＝S、CRR'、SO、SO ₂ P (O) R, siRR 'and GeRR';

wherein at least one of the following conditions is true:

wherein if L is aryl, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

wherein any two adjacent substituents may be fused or joined to form a ring; and is also provided with

Wherein the compound is not

2. The compound of claim 1, wherein the compound has the structure of formula II:

wherein each R is ¹ 、R ² 、R ³ And R is ⁴ Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

wherein R is ¹ 、R ² 、R ³ And R is ⁴ At least one of them is-L-SiAr ¹ Ar ² Ar ³ And R is ^A 、R ¹ 、R ² 、R ³ And R is ⁴ At least one of them is-NR ⁵ R ⁶ The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

Wherein any two adjacent substituents may be fused or joined to form a ring.

3. The compound of claim 2, wherein each R, R', R ^A 、R ¹ 、R ² 、R ³ 、R ⁴ 、Ar ¹ 、Ar ² And Ar is a group ³ Independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and/or wherein Ar ¹ 、Ar ² And Ar is a group ³ Each independently selected from the group consisting of: alkyl, cycloalkyl, heteroalkyl, aryl, heteroaryl, and combinations thereof, which may be further substituted.

4. The compound of claim 1, wherein Y ^A Is O, or Y ^A Is S, or Y ^A Is Se, or Y ^A Is NR; or wherein Y ^A Is NR and R ^A At least one of which is a substituted biscarbazolyl group comprising silane; or wherein Y ^A Is NR and R ^A At least one of which is a substituted silane-containing compoundA dicarbazolyl group, and wherein Si in the silane is directly attached to the dicarbazolyl moiety.

5. The compound of claim 1, wherein R ^A At least one of (a) is a carbazole moiety substituted with at least one group comprising silane and at least one substituted or unsubstituted carbazole, wherein R ^A Is a carbazole moiety substituted with at least one group comprising a silane and at least one substituted or unsubstituted carbazole, and wherein Si in the silane is directly connected to the carbazole moiety.

6. The compound according to claim 1, wherein X ¹ -X ⁸ Each is C and X ¹ -X ⁴ At least one of the groups-L-SiAr ¹ Ar ² Ar ³ Substituted and X ¹ -X ⁸ At least one of the warp groups NR ⁵ R ⁶ Substitution; provided that if Y ^A Is O and X ⁴ Through SiPh ₃ Substituted, then X ⁵ -X ⁸ One of which is NR via said group ⁵ R ⁶ Substitution; or wherein L is a direct bond.

7. The compound of claim 1, wherein R ⁷ And R is ⁸ Are each a 6-membered aromatic or heteroaromatic ring, or wherein R ⁷ And R is ⁸ Are linked to form a carbazolyl group.

8. The compound according to claim 1, wherein X ¹ via-SiAr ¹ Ar ² Ar ³ Substituted, or wherein X ⁴ via-SiAr ¹ Ar ² Ar ³ And (3) substitution.

9. The compound of claim 1, wherein the compound is selected from the group consisting of:

wherein Y is ^B Selected from S and Se;

wherein T is ¹ To T ⁸ Each independently is C or N;

wherein T is ¹ To T ⁸ At least one of which is N;

wherein X is ¹ To X ²⁴ Each independently is C or N;

wherein L' is a substituted or unsubstituted aryl or heteroaryl group;

R ¹ 、R ^B '、R ^C ' and R ^B To R ^I Each independently is hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; wherein any two adjacent substituents may be fused or joined to form a ring.

10. The compound of claim 1, wherein the compound is selected from the group consisting of:

/>

wherein Y1 to Y141 are NR1 to NR141, Y142 is S, Y143 is Se, and Y144 is O, and,

wherein R1 to R141 are defined in the following list:

/>

wherein C1 to C15 are defined in the following list:

/>

11. the compound of claim 1, wherein the compound is selected from the group consisting of the compounds in the following list a:

/>

12. an organic light emitting device OLED comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound of formula I:

wherein X is ¹ -X ⁸ Each independently is C or N;

Wherein at least one of the following conditions is true:

1)X ¹ -X ⁸ at least one of which is N andand R is ^A At least one of which is a substituted biscarbazolyl group comprising silane;

wherein if L is aryl, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

wherein each R is ⁷ And R is ⁸ Independently an optionally further substituted 5-or 6-membered aromatic or heteroaromaticA family ring;

Wherein the compound is not

13. The OLED of claim 12, wherein the compound is a host and the organic layer is an emissive layer comprising a phosphorescent emitter.

14. The OLED of claim 12, wherein the compound is a host and the OLED comprises as an emitter an acceptor and a sensitizer selected from the group consisting of delayed fluorescent materials, phosphorescent materials, and combinations thereof; wherein the sensitizer transfers energy to the receptor.

15. A consumer product comprising an organic light emitting device OLED, the organic light emitting device comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode,

wherein the organic layer comprises a compound of formula I:

wherein X is ¹ -X ⁸ Each independently is C or N;

C＝NR、C＝CRR'、C＝S、CRR'、SO、SO ₂ P (O) R, siRR 'and GeRR';

each of which is provided withR is a number of ^A R and R' are independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

wherein at least one of the following conditions is true:

wherein if L is aryl, then R ⁵ menstrual-NR ⁷ R ⁸ Substitution;

Wherein the compound is not

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