CN117624247A

CN117624247A - Organic electroluminescent material and device

Info

Publication number: CN117624247A
Application number: CN202311119844.3A
Authority: CN
Inventors: 伯特·阿莱恩; V·古迪帕蒂; V·赫格德; 皮埃尔·吕克·T·布德罗
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2022-09-01
Filing date: 2023-09-01
Publication date: 2024-03-01

Abstract

The present application relates to organic electroluminescent materials and devices. There is provided a deuterated compound produced by a method comprising the steps of: heating a first compound to an elevated temperature in a solvent containing a deuterated material to produce the deuterated compound; isolating the deuterated compound; wherein the first compound has a solubility in the deuterated material of at least 0.01mg/mL at 25 ℃. OLEDs and consumer products containing the deuterated compounds are also provided.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application claims priority from 35u.s.c. ≡119 (e) to the following U.S. provisional applications: 63/403,169 as filed on 1 month 2022, 63/426,729 as filed on 11 month 2022, 63/432,083 as filed on 13 month 2022, 63/442,524 as filed on 1 month 2023, and 63/503,984 as filed on 24 month 2023, all of which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates generally to deuterated organometallic compounds and formulations and various uses thereof, including as 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 deuterated compound produced by a process comprising: heating a first compound to an elevated temperature in a solvent containing a deuterated material to produce a deuterated compound; isolating the deuterated compound; wherein the first compound has a solubility of at least 0.01mg/mL in deuterated material at 25 ℃; and wherein the elevated temperature is at least 50 ℃ and at most T ^D Wherein T is ^D Is the boiling point of the solvent.

In another aspect, the present disclosure provides a deuterated compound comprising an aromatic ring coordinated to a metal via a direct bond or a single atom connection group; wherein the aromatic ring is substituted with at least one D (deuterium) and at least one substituent selected from the group consisting of: 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, borane, and combinations thereof; and wherein at least one substituent may be joined or fused to another substituent in the compound to form a ring.

In yet another aspect, the present disclosure provides a formulation comprising a deuterated compound as described herein.

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

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a deuterated 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 "selenoalkyl" refers to-SeR _s Radicals (C)

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 ) ₃ 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 "germyl" refers to-Ge (R _s ) ₃ A group wherein each R _s May be the same or different.

The term "borane" refers to-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 from 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 essentially 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 may be 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, diazole, 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 pyridine, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1-boron-nitrogen, 1-nitrogen, 4-boron-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, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenkyl, sulfinyl, sulfonyl, phosphino, 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, borane, 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, 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 When two are substituted, 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

The present disclosure provides deuterated cyclometallated complex compounds obtained from methods for making such complex compounds. In contrast to the ligands used to form the metal complex, proton-deuterium exchange occurs on the metal complex. Deuteration using this method allows exchange of sites on the net ligand that do not normally occur. Thus, the products resulting from this process are unique to this process and are not readily produced via deuteration exchange of the corresponding ligands, and deuteration of the metal complexes at specific positions can result in an extended lifetime of the OLED devices produced using such metal complexes. Deuterated emitter molecules have been thought to enhance device lifetime performance. However, hydrogen deuteration does not yield the same advantage of lifetime performance at every location. During degradation of the device, only those hydrogen atoms with the greatest activity have a significant impact on performance. For example, in phosphorescent emitters, the positions of the hydrogen atoms with maximum activity in the metal complex may be different from those in the ligand due to the change in the central metal environment, and it is sometimes difficult to predict which position of the hydrogen atoms has the maximum activity. The advances described herein provide great advantages for obtaining a final emitter complex with the most active hydrogen atoms to be deuterated without searching for hydrogen atoms that need to be deuterated, as the disclosed deuteration method will first occur at the hydrogen sites with the greatest chemical activity. Thus, this process is very different from conventional pre-designed deuteration processes, which typically deuterate the entire aromatic ring or extremely specific alkyl groups. Conventional methods are generally performed according to the feasibility of synthetic routes to obtain specific deuterated groups and not according to the hydrogen activity of the final emitter complex. As a result, surprisingly, the most active hydrogen sites in emitter complexes (e.g., metal complexes of phosphorescent emitters) differ greatly from those previously thought.

In some embodiments, the first compound is a metal coordination compound. In some embodiments, the first compound is capable of functioning as an emitter, a host, a barrier layer material, a transport layer material, or an injection layer material in an organic light emitting device at room temperature. In some embodiments, the first compound may be a partially deuterated compound.

In some embodiments, the deuterated material is entirely deuterated. In some embodiments, the deuterated material is partially deuterated. It is understood that a solvent containing a deuterated material of the present disclosure may refer to a deuterated solvent, and it may refer to a partially deuterated solvent (if it contains a non-deuterated material). When it contains only deuterated material, the solvent may also refer to a partially deuterated solvent (if the deuterated material is partially deuterated) or a fully deuterated solvent (if the deuterated material is fully deuterated).

In some embodiments, the deuterated material is selected from the group consisting of: d, d ⁶ Dimethyl sulfoxide, CD ₃ OD (d 4-methanol), CD ₃ CD ₂ OD (d 6-ethanol), C ₆ D ₆ (d 6-benzene), C ₇ D ₈ (d 8-A)Benzene), D4-acetic acid, D6-acetone, D3-acetonitrile, D12-cyclohexane, D ₂ O, d7-N, N-dimethylformamide, d8-1, 4-dioxane, d 2-dichloromethane, d 5-pyridine, d 8-tetrahydrofuran, d-trifluoroacetic acid, d 3-trifluoroethanol, and combinations thereof. In some embodiments, the solvent contains only deuterated materials. In some such embodiments, the deuterated material may be one or a combination of the above. In some embodiments, the solvent further comprises a non-deuterated material. The non-deuterated material may be any organic solvent used in common reactions. The non-deuterated material may be, for example, but is not limited to, any of the non-deuterated forms of the deuterated materials described above.

In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.025 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.05 mg/mL. In some embodiments, the first compound has a solubility of at least 0.075mg/mL in the deuterated solvent. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.10 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.25 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.50 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 0.75 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 1.0 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 2.0 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 3.0 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 4.0 mg/mL. In some embodiments, the first compound has a solubility in the deuterated solvent of at least 5.0 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.025 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.05 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.075 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.10 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.25 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.50 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 0.75 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 1.0 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 2.0 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 3.0 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 4.0 mg/mL. In some embodiments, the first compound has a solubility in the solvent of at least 5.0 mg/mL.

In some embodiments, the elevated temperature is the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 5 ℃ higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 10 ℃ higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 15 ℃ higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 20 ℃ higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 25 ℃ higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is the temperature at which the deuterated material boils.

In some embodiments, the elevated temperature is at least 75 ℃ and at most T ^D . In some embodiments, the elevated temperature is at least 100 ℃ and at most T ^D . In some embodiments, the elevated temperature is at least 125 ℃ and at most T ^D . In some embodiments, the elevated temperature is at least 150 ℃ and at most T ^D . In some embodiments, the elevated temperature is not less than T ^D -80 ℃. In some embodiments, the elevated temperature is not less than T ^D -70 ℃. In some embodiments, the elevated temperature is not less than T ^D -60 ℃. In some embodiments, the elevated temperature is not less than T ^D -50 ℃. In some embodiments, the elevated temperature is not less than T ^D -40 ℃. In some embodiments, the elevated temperature is not less than T ^D -30 ℃. In some embodiments, the elevated temperature is not less than T ^D -20 ℃. In some embodimentsIn the example, the elevated temperature is not lower than T ^D -10℃。

In some embodiments, the methods described herein produce deuterated compounds in at least 50% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 60% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 70% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 80% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 90% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 95% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 98% yield. In some embodiments, the methods described herein produce deuterated compounds in at least 99% yield.

In some embodiments, wherein the first compound has two or more H atoms. In some embodiments, the first compound has one or more non-aromatic H atoms and one or more aromatic rings having H atoms.

In some embodiments, at least two H atoms in the deuterated compound are replaced with D as compared to the first compound.

In some embodiments, at least one aromatic H in the deuterated compound is replaced with D as compared to the first compound. In some embodiments, at least two of the aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least three of the aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least four aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least five of the aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, the aromatic ring of the deuterated compound is completely deuterated.

In some embodiments, at least one non-aromatic H in the deuterated compound is replaced with D as compared to the first compound. In some embodiments, at least two non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least three non-aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least four non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least five non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least six non-aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least seven non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least eight non-aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least nine non-aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least ten non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least eleven of the non-aromatic H in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, at least twelve non-aromatic H's in the deuterated compound are replaced with D as compared to the first compound. In some embodiments, all non-aromatic H in the deuterated compound is replaced with D.

In some embodiments, at least two H's located on the same carbon atom in the deuterated compound are replaced with D as compared to the first compound.

In some embodiments, at least two H on two different carbon atoms in the deuterated compound are replaced with D as compared to the first compound.

In some embodiments, at least one H located on the aromatic ring in the deuterated compound is replaced with D as compared to the first compound; and wherein the aromatic ring is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole; and wherein the aromatic ring may be further condensed or substituted.

In some embodiments, the deuterated compound is a single compound. In some embodiments, the deuterated compound is a mixture having different moieties that are partially deuterated. In some embodiments, the mixing ratio of the different portions with portions deuterated can be controlled by, for example, controlling the temperature.

In some embodiments, the elevated temperature is maintained for at least 30 minutes. In some embodiments, the elevated temperature is maintained for at least 1 hour. In some embodiments, the elevated temperature is maintained for at least 5 hours. In some embodiments, the elevated temperature is maintained for at least 10 hours. In some embodiments, the elevated temperature is maintained for at least 15 hours. In some embodiments, the elevated temperature is maintained for at least 20 hours. In some embodiments, the elevated temperature is maintained for at least 24 hours. In some embodiments, the elevated temperature is maintained for at least 36 hours. In some embodiments, the elevated temperature is maintained for at least 48 hours.

In some embodiments, the method further comprises heating the first compound in a solvent comprising the deuterated material and a base. In some such embodiments, the base may be selected from the group consisting of: sodium hydride, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate.

In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 5mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 10mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 20mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 30mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 40mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 50mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 60mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 70mm Hg above atmospheric pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing the deuterated material at a pressure at least 76mm Hg above atmospheric pressure. In some such embodiments, the solvent is partially deuterated. In some of these embodiments, the solvent is completely deuterated.

In some embodiments, the deuterated compound is capable of emitting light from a triplet excited state to a singlet ground state in an OLED at room temperature.

In some embodiments, the deuterated compound is a metal-coordination complex having a metal-carbon bond.

In some embodiments, the deuterated compound is a metal-coordination complex having a metal-carbene bond.

In some embodiments, the deuterated compound is a metal-coordination complex having a metal-nitrogen bond.

In some embodiments, the deuterated compound is a metal-coordination complex having a metal-oxygen bond or a metal-sulfur bond.

In some embodiments, the metal is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au, ag and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt.

In some embodiments, the deuterated 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 in the following list A1:

/>

wherein L is ² And L ³ Each independently selected from the group consisting of the structures in the following list B1:

/>

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

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

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

wherein Y' is selected from the group consisting of: b R _e 、N R _e 、P R _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f ；

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

wherein each R is _a 、R _b 、R _c And R is _d Can independently represent monosubstituted to the largest possible number of substituted or unsubstituted;

wherein each R is _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, L ¹ Selected from the group consisting of the following structures (list A2):

/>

wherein R is _a '、R _b '、R _c '、R _d ' and R _e ' each independently represents zero, a single, or at most the maximum allowable number of substitutions to its associated ring;

wherein R is _a '、R _b '、R _c '、R _d ' and R _e ' each independently is hydrogen or a substituent selected from the group consisting of the universal substituents defined herein; and is also provided with

Wherein R is _a '、R _b '、R _c '、R _d ' and R _e Any two of the' may be fused or joined to form a ring or to form a multidentate ligand.

In some embodiments, the deuterated compound 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 May be linked to form a tetradentate ligand in the Pt compound.

It should be understood that in the above examples and throughout this disclosure, L _A May be L ¹ And L is _B And L _C Can each independently be L ² Or L ³ 。

In some embodiments, the deuterated compound is a hexadentate Ir complex comprising three bidentate ligands, wherein at least one bidentate ligand is a substituted or unsubstituted phenylpyridine ligand, or a substituted or unsubstituted acetylacetonate ligand.

In some embodiments, the deuterated compound is a tetradentate Pt complex comprising at least one Pt-carbene bond or Pt-O bond.

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1a below:

/>

wherein the method comprises the steps of

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;

R ^10a 、R ^20a 、R ^30a 、R ^40a and R is ^50a Independently represents a single substitution up to a maximum of substitution, or no substitution;

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 and R is ⁹⁹ Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, selenium Alkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and at least one substituent of the above structures is D.

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1b below:

/>

wherein:

l is independently selected from the group consisting of: direct bond, 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 selected at each occurrence from the group consisting of O, S, se, NR "and CR" R' ";

each R is ^A" 、R ^B" 、R ^C" 、R ^D" 、R ^E" And R is ^F" Independently represent monosubstitutedUp to a maximum of substitution, or no substitution;

R、R'、R"、R"'、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 is ^N" Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, combinations thereof; and at least one substituent of the above structures is D.

In some embodiments, the deuterated compound is a tetradentate Pt complex comprising a tetradentate ligand;

wherein the tetradentate ligand comprises at least one six-membered aryl or heteroaryl group coordinated to Pt; wherein at least one six-membered aryl or heteroaryl is partially or fully deuterated; and is also provided with

Wherein at least one six-membered aryl or heteroaryl group may be further fused or substituted.

In some of the above embodiments, the at least one six-membered aryl or heteroaryl is selected from the group consisting of: phenyl, pyridine, pyrimidine, pyrazine, pyridazine and triazine. In some of the above embodiments, the at least one six membered heteroaryl is pyridine.

In some of the above embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1c below:

/>

wherein:

Each R is ^A" 、R ^B" 、R ^C" 、R ^D" 、R ^E" And R is ^F" Independently represents monosubstituted up to a maximum of substituted or unsubstituted;

R、R'、R"、R"'、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 is ^N" Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, combinations thereof;

wherein one or more substituents bonded to the fused or unfused phenyl or pyridine ring in the various structures described above is D.

In some of the above embodiments, the deuterated compound has the formula

Wherein R is ^B" Or R is ^C" One or more of which is D. In some of the above embodiments, exactly one R ^B" Or R is ^C" Is D. In some of the above embodiments, two R ^B" Or R is ^C" Is D. In some of the above embodiments, D is meta to N in the pyridine. In some of the above embodiments, one R ^B" In the para position of N. In some of the above embodiments, one R ^B" Selected from the group consisting of: aryl, heteroaryl, alkyl, cycloalkyl, silyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1 below:

/>

wherein the variables are as defined above.

In some embodiments, the deuterated compound is selected from the group consisting of the structures in list 2 below:

/>

in some embodiments, the deuterated compound is capable of acting as a delayed fluorescence emitter in an OLED at room temperature.

In some embodiments, the deuterated compound is capable of acting as a thermally activated delayed fluorescence emitter in an OLED at room temperature.

In some embodiments, the deuterated compound comprises at least one donor group and at least one acceptor group.

In some embodiments, the deuterated compound is a metal complex.

In some embodiments, the deuterated compound is a non-metal complex.

In some embodiments, the deuterated compound is a Cu, ag, or Au complex.

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

wherein X is selected from the group consisting of: o, S, se and NR;

wherein each R may be the same or different and each R is independently an acceptor group, an organic linking group bonded to an 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

Wherein each R 'may be the same or different and each R' is independently selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In some embodiments, the deuterated compound comprises at least one chemical moiety selected from the group consisting of: nitrile, isonitrile, borane, fluoro, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole.

In some embodiments, the deuterated compound is capable of acting as a fluorescent emitter in an OLED at room temperature.

In some embodiments, the deuterated compound comprises at least one organic group selected from the group consisting of:

and aza analogues thereof;

wherein a is selected from the group consisting of: o, S, se, NR ' and CR ' R ';

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

/>

Wherein R is ¹ To R ⁵ Each independently represents a single substitution to the maximum possible number of substitutions, or no substitution;

wherein R is ¹ To R ⁵ Each independently is 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, borane, and combinations thereof.

In another aspect, the present disclosure also provides a compound capable of functioning as an emitter in an organic light emitting device at room temperature; wherein the compound has at least one carbocycle or heterocycle carrying at least two substituents, one of which is deuterium and the remaining one of which is not hydrogen or deuterium. In some embodiments, the emitter is selected from the group consisting of phosphorescent emitters, delayed fluorescent emitters, fluorescent emitters. In some embodiments, the fluorescent emitter may be a singlet or a doublet emitter. In some such embodiments, the singlet emitter may also comprise a TADF emitter. In some embodiments, at least one carbocycle or heterocycle is an aryl or heteroaryl ring. In some embodiments, the remaining one of the at least two substituents is a universal substituent as described herein other than deuterium. In some embodiments, the remaining one of the at least two substituents is a preferred, more preferred, or most preferred substituent other than deuterium as described herein. In some embodiments, the remaining one of the at least two substituents is a non-deuterated, partially or fully deuterated alkyl or cycloalkyl. In some embodiments, the remaining one of the at least two substituents is a non-deuterated, partially or fully deuterated phenyl group. In some embodiments, the compound is a tetradentate Pt or Pd complex comprising a tetradentate ligand, or a hexadentate Ir complex comprising three bidentate ligands; wherein the tetradentate ligand and at least one bidentate ligand comprise at least one carbocycle or heterocycle carrying at least two substituents as described herein. In some embodiments, such carbocycles or heterocycles are six-membered aryl or heteroaryl groups coordinated to Pt, pd or Ir.

In some of the above embodiments, the six-membered aryl or heteroaryl is selected from the group consisting of: phenyl, pyridine, pyrimidine, pyrazine, pyridazine and triazine. In some of the above embodiments, the six-membered aryl is phenyl and the six-membered heteroaryl is pyridine.

In some of the above embodiments, the compound has a formula selected from the group consisting of:

/>

wherein:

In some of the above embodiments, the compound has the formula

Wherein R is ^B" Or R is ^C" One or more of which is D. In some of the above embodiments, exactly one R ^B” Or R is ^C” Is D. In some of the above embodiments, two R ^B” Or R is ^C” Is D. In some of the above embodiments, D is meta to N in pyridine. In some of the above embodiments, one R ^B" In the para position of N. In some of the above embodiments, one R ^B" Selected from the group consisting of: aryl, heteroaryl, alkyl, cycloalkyl, silyl, and moieties thereofA partially or fully deuterated variant, a partially or fully fluorinated variant thereof, and combinations thereof.

In another aspect, the present disclosure also provides deuterated compounds comprising an aromatic ring coordinated to a metal via a direct bond or a single atom linking group;

wherein the aromatic ring is substituted with at least one D and at least one substituent selected from the group consisting of: 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, borane, and combinations thereof; and is also provided with

Wherein at least one substituent may be joined or fused to another substituent in the compound to form a ring.

It is understood that a single atom linking group means that the linking atom is one atom, such as BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr, c=crr', s= O, SO ₂ CR, CRR ', siRR', geRR ', wherein R and R' are each independently hydrogen or a substituent selected from the group consisting of universal substituents as defined herein.

In some embodiments, the aromatic ring is a benzene ring directly coordinated to the metal. In some embodiments, the aromatic ring is a benzene ring coordinated to the metal via an O or S linking group. In some embodiments, the aromatic ring is a pyridine ring that is directly coordinated to the metal.

In some embodiments, the metal is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au, ag and Cu.

In some embodiments, the deuterated compound is capable of acting as a phosphorescent emitter in an organic light emitting device at room temperature.

In some embodiments, the aromatic ring is a 5-or 6-membered aryl or heteroaryl ring.

In some embodiments, the aromatic ring is substituted with at least two D.

In some embodiments, the aromatic ring is substituted with at least three D.

In some embodiments, the aromatic ring is substituted with at least two substituents independently selected from the group consisting of: 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, borane, and combinations thereof.

In some embodiments, at least one substituent is partially or fully deuterated or partially or fully fluorinated.

In some embodiments, at least one substituent is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, silyl, fluoro, and nitrile.

In some embodiments, at least one substituent is joined or fused to another substituent in the compound to form a ring fused to an aromatic ring.

In some embodiments, the metal is Ir.

In some embodiments, the metal is Pt.

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 manifest A1 as defined herein;

wherein L is ² And L ³ Independently selected from the group consisting of list B1 as defined herein.

In some embodiments, L ¹ Selected from the group consisting of manifest A2 as defined herein.

In some embodiments, the compound 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;

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1a as defined herein.

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1b as defined herein.

In some embodiments, the deuterated compound is a tetradentate Pt complex comprising a tetradentate ligand; wherein the tetradentate ligand comprises at least one six-membered aryl or heteroaryl group coordinated to Pt; wherein the at least one six-membered aryl or heteroaryl is partially or fully deuterated; and is also provided with

In some embodiments, the at least one six-membered aryl or heteroaryl is selected from the group consisting of: phenyl, pyridine, pyrimidine, pyrazine, pyridazine and triazine.

In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in list 1c as defined herein.

In some embodiments, the deuterated compound has the formula

Wherein R is ^B" Or R is ^C" One or more of which is D.

In some embodiments, in the structure of list 1b or 1c, at least one R ^C" Is D, and at least one R ^C" Not H or D. In some such embodiments two R' s ^C" Is D, and the remaining two R ^C" Not H or D. In some such embodiments, two R's of D ^C" In the meta-position to the carbon atom substituted by the oxygen atom. In some such embodiments, two R's are in meta-position to the carbon atom bound to the imidazole ring ^C" Is an alkyl group having at least two, three, four or five carbon atoms. In some casesIn an embodiment, at least one R ^B" Is D, and at least one R ^B" Not H or D. In some such embodiments, two R' s ^B" Is D, and one R ^B" Not H or D. In some such embodiments, two R's of D ^B" In the meta position of the N atom in pyridine. In some embodiments, R is para to N in pyridine ^B" Is a substituted or unsubstituted phenyl group. In some such embodiments, the substituted phenyl may be partially or fully deuterated, or partially or fully fluorinated. In some such embodiments, the substituted phenyl is substituted with at least one silane or germanyl group.

In some embodiments, R ^A1" Selected from the group consisting of:

in some embodiments of the present invention, in some embodiments,part G in the structure is selected from the group consisting of: />

In some embodiments of the present invention, in some embodiments,the moiety H in the structure is selected from the group consisting of: />

/>

In some embodiments, the compound has the formula:wherein R is ^A1" Part G and part H are as described above, R ^T Selected from the group consisting of: />And R is ^Y Selected from the group consisting of: />

In some embodiments, the compound has the formula Pt- (R) corresponding to the structure described above _Ax )(R _Ty )(R _Yz )(G _p )(H _q ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is an integer from 1 to 21, y is an integer from 1 to 4, z is an integer from 1 to 8,p, q is an integer from 1 to 12, and q is an integer from 1 to 43; and the compound is selected from Pt- (R) _A1 )(R _T1 )(R _Y1 )(G ₁ )(H ₁ ) To Pt- (R) _A21 )(R _T4 )(R _Y8 )(G ₁₂ )(H ₄₃ ) A group of groups.

In some embodiments, the deuterated compound is selected from the group consisting of list 1 as defined herein.

In some of the above embodiments, the deuterated compound is selected from the group consisting of list 2 as defined herein.

In yet another aspect, the present disclosure further provides deuterated Pt or Pd compounds. Deuterated compounds contain an aromatic ring coordinated to Pt or Pd via a direct bond or a single atom linking group; wherein the aromatic ring is substituted with at least one D.

In some embodiments, the deuterated compound comprises a five-membered heteroaryl coordinated to Pt or Pd. In some embodiments, the five-membered heteroaryl is an imidazole or imidazole-derived carbene. In some embodiments, the aromatic ring is substituted with at least two D. In some embodiments, the aromatic ring is partially deuterated. In some embodiments, the aromatic ring is a benzene ring directly coordinated to the metal. In some embodiments, the aromatic ring is a benzene ring coordinated to the metal via an O or S linking group. In some embodiments, the aromatic ring is a pyridine ring that is directly coordinated to the metal.

In some embodiments, a deuterated compound as 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 percentages of possible hydrogen atoms (e.g., hydrogen or deuterium sites) replaced by deuterium atoms.

In the presence of a compound having the formula M (L ¹ ) _x (L ² ) _y (L ³ ) _z In some embodiments of the heteroleptic compounds of (2), wherein ligand L ¹ Having a first substituent R ^I Wherein the first substituent R ^I a-I at ligand L ¹ Is furthest from the metal M among all atoms of (a). In addition, ligand L ² Having a second substituent R when present ^II Wherein the second substituent R ^II a-II at ligand L ² Is furthest from the metal M among all atoms of (a). In addition, ligand L ³ Having a third substituent R when present ^III Wherein the third substituent R ^III The first atom a-III in the ligand L ³ Is furthest from the metal M among all atoms of (a).

In such heteroleptic compounds, the vector V can be defined _D1 、V _D2 And V _D3 It is defined as follows. V (V) _D1 Represents the direction from the metal M to the first atom a-I, and the vector V _D1 Value D of (2) ¹ Represents a metal M and a first substituent R ^I a-I, the first atom a-I of the group. V (V) _D2 Represents the direction from the metal M to the first atom a-II and the vector V _D2 Value D of (2) ² Represents a metal M and a second substituent R ^II a-II, the first atom a-II. V (V) _D3 Represents the direction from the metal M to the first atom a-III, and the vector V _D3 Value D of (2) ³ Represents a metal M and a third substituent R ^III a-III, and a linear distance between the first atoms a-III.

In such heteroleptic compounds, spheres are defined having a radius R centered at the metal M and the radius R is that which allows the spheres to enclose compounds in which not substituents R ^I 、R ^II And R is ^III A minimum radius of all atoms of a portion of (a); and wherein D ¹ 、D ² And D ³ At least one of which is larger than the radius r by at leastIn some embodiments, D ¹ 、D ² And D ³ At least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or +.>

In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis and defines a transition dipole moment axis and a vector V _D1 、V _D2 And V _D3 Angle between the transition dipole moment axis and vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 40 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 30 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 20. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 10 °. In some embodiments of the present invention, in some embodiments, Transition dipole moment axis and vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 20. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 15. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 10.

In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 All three angles in between are less than 20 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 All three angles in between are less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 All three angles in between are less than 10 °.

In some embodiments of such heteroleptic compounds, the compounds have a Vertical Dipole Ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.30 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.25 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.20 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.15 or less.

The meaning of the term transition dipole moment axis of a compound and the perpendicular dipole ratio of the compound will be readily understood by those of ordinary skill in the art. However, the meaning of these terms can be found in U.S. patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. U.S. patent No. 10,672,997 discusses the Horizontal Dipole Ratio (HDR) of a compound, rather than VDR. However, one skilled in the art will readily appreciate vdr=1-HDR.

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 the deuterated compounds disclosed in the above-described compounds section of the present disclosure.

In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound as described herein.

In some embodiments, the organic layer may be an emissive layer and the deuterated compound as described herein may be an emissive dopant or a non-emissive dopant.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene comprising a benzofused thiophene or benzofused furan, wherein any substituent in the host is a non-fused substituent 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 With Ar ₂ Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ ² Benzo [ d ]]Benzo [4,5 ]]Imidazo [3,2-a]Imidazole, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de]Anthracene, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ ² Benzo [ d ]]Benzo [4,5 ]]Imidazo [3,2-a]Imidazole and aza- (5, 9-dioxa-13 b-boronaphtho [3,2, 1-de)]Anthracene).

In some embodiments, the subject may be selected from a subject group 1 consisting of:

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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: absence, one 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 the' independentlyRepresents monosubstituted up to a maximum of substituted or unsubstituted;

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, germanyl, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, borane, and combinations thereof; and is also provided with

R ^A '、R ^B '、R ^C '、R ^D '、R ^E '、R ^F ' and R ^G Adjacent two of the' are optionally joined or fused to form a ring.

In some embodiments, the subject may be selected from a subject group 2 consisting of:

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/> and combinations thereof.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

In some embodiments, the emissive layer may include two hosts: a first body and a second body. In some embodiments, the first body is a hole transporting body and the second body is an electron transporting body. In some embodiments, the first body and the second body may form an excitation complex.

In some embodiments, a compound as described herein may be a sensitizer; wherein the device may further comprise a recipient; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, 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 portion 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 over the organic emissive layer serves as the enhancement layer. The enhancement layer includes a plasmonic material exhibiting surface plasmon resonance, the plasmonic material non-radiatively coupled to the emitter material and transferring excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is disposed no further than a threshold distance from the organic emissive layer, wherein the emitter material has 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 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 an opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emission layer from the enhancement layer, but is still able to outcouple energy 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 as photons. In other embodiments, energy is scattered from surface plasmon modes of the device into other modes, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered to 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 intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and/or mixtures of these materials.

The enhancement layer alters the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, altered emission linearity, altered emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced OLED device roll-off efficiency. Placing the enhancement layer on the cathode side, the anode side, or both sides creates an OLED device that takes advantage of any of the effects described 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 disclosure may also include any other functional layers common in OLEDs.

The enhancement layer may comprise a plasmonic material, an optically active super-structured material or a hyperbolic super-structured material. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic 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. Generally, a metamaterial is a medium composed of different materials, wherein the overall effect of the medium is different from the sum of its material portions. In particular, we define an optically active super-structured material as a material having both negative permittivity and negative permeability. On the other hand, hyperbolic metamaterials are anisotropic media in which the permittivity or permeability has different signs for different spatial directions. Optically active and hyperbolic metamaterials are very different from many other photonic structures, such as 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 terms that will be understood by those skilled in the art: the dielectric constant of a metamaterial in the propagation direction can be described by an effective dielectric approximation. Plasmonic and super-structured materials provide a method for 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 wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.

In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized 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 over the material. In these embodiments, the outcoupling may be adjusted by at least one of the following means: 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 a shell coated with another 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 additional layers disposed over them. In some embodiments, the polarization of the emission may be adjusted using an outcoupling layer. Changing the size and periodicity of the outcoupling layer may select the type of polarization that preferentially outcouples 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, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise claim 1 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. The 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 blocking 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 luminescent 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 molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. 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 compounds may be used as a phosphor-photosensitizing agent in an OLED, where one or more layers in the OLED contain receptors in the form of one or more fluorescent and/or delayed fluorescent emitters. In some embodiments, the compound may be used as a component of an exciplex to be used as a sensitizer. As a phosphorus photosensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The receptor concentration may be in the range of 0.001% to 100%. The acceptor may be in the same layer as the phosphorus photosensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be produced by any or all of the sensitizer, acceptor, and final emitter.

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 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:

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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, 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, 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, iso- Nitrile, 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 from 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 of 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 of 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; a group consisting of aromatic heterocyclic compounds such as: 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, 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 option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium (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 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 an integer from 0 to 20 or from 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 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 from 1 to 20; l (L) ¹⁰¹ Is another ligand, and k' is an integer from 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 contains (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 for purposes of example only and are not intended to limit the scope of the present 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.

It should also be understood that the different embodiments of all compounds and devices described herein are interchangeable if applicable in other aspects of the disclosure as a whole.

Experimental data

The following examples have been made using the methods described herein. The final product has passed ¹ H NMR confirmed.

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Claims

1. A deuterated compound comprising:

an aromatic ring coordinated to the metal via a direct bond or a monoatomic linking group;

Wherein the at least one substituent may be joined or fused to another substituent in the compound to form a ring.

2. The deuterated compound of claim 1 wherein the metal is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au, ag and Cu.

3. The deuterated compound of claim 1, wherein the compound is capable of functioning as a phosphorescent emitter in an organic light emitting device at room temperature.

4. The deuterated compound of claim 1 wherein the aromatic ring is a 5-or 6-membered aryl or heteroaryl ring; and/or

Wherein the aromatic ring is substituted with at least two D; and/or the aromatic ring is substituted with at least two substituents independently selected from the group consisting of: 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, borane, and combinations thereof.

5. The deuterated compound of claim 1 wherein the at least one substituent is partially or fully deuterated or partially or fully fluorinated; and/or

Wherein the at least one substituent is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, silyl, fluoro and nitrile; and/or

Wherein the at least one substituent is joined or fused to another substituent in the compound to form a ring fused to the aromatic ring.

6. The deuterated compound according to claim 1 wherein the deuterated compound has 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:

wherein L is ² And L ³ Each independently selected from the group consisting of:

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

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

7. The deuterated compound of claim 6, wherein the compound 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;

8. The deuterated compound according to claim 1 wherein the deuterated compound is a tetradentate Pt complex comprising at least one Pt-carbene or Pt-O bond.

9. The deuterated compound of claim 1, wherein the deuterated compound has a formula selected from the group consisting of:

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wherein the method comprises the steps of

X ⁹⁶ To X ⁹⁹ Is independently C or N;

R ^10a 、R ^20a 、R ^30a 、R ^40a 、R ^50a 、R ^A" 、R ^B" 、R ^C" 、R ^D" 、R ^E" and R is ^F" Independently represents a single substitution up to a maximum of substitution or no substitution;

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 is ^N" Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least one substituent in the above structures is D; and is also provided with

One or more substituents bonded to the fused or unfused phenyl or pyridine ring in the various structures described above are D.

10. The deuterated compound according to claim 9 wherein the deuterated compound has the formula (la)

Wherein R is ^B" Or R is ^C" One or more of which is D.

11. The deuterated compound according to claim 9 wherein two R are meta to the carbon atom bound to the imidazole ring ^C" Is an alkyl group having at least two or more carbon atoms; and/or R wherein R is para to N in pyridine ^B" Is a substituted or unsubstituted phenyl group.

12. The deuterated compound of claim 11, wherein the substituted phenyl group is partially or fully deuterated or partially or fully fluorinated; and/or wherein the substituted phenyl is substituted with at least one silane or germanyl group.

13. The deuterated compound of claim 9, wherein the deuterated compound has a formula selected from the group consisting of: />

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14. An 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 the deuterated compound of claim 1.

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

an anode;

a cathode; and