CN117229327A

CN117229327A - Organic electroluminescent material and device

Info

Publication number: CN117229327A
Application number: CN202310710181.6A
Authority: CN
Inventors: 埃里克·A·玛格里斯; 格扎·西盖蒂; I·米拉斯; N·J·汤普森; 亨利·C·赫博尔; 姬志强
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2022-06-15
Filing date: 2023-06-15
Publication date: 2023-12-15

Abstract

The present application relates to organic electroluminescent materials and devices. The present disclosure provides a metal coordination complex compound. The metal complex compound is capable of functioning as an emitter in an organic light emitting device OLED at room temperature and has a vertical dipole ratio VDR in the OLED of greater than 0.33. Formulations, OLEDs and consumer products comprising the metal complex compounds are also provided.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application is based on 35 U.S. c. ≡119 (e) claiming priority from U.S. provisional application No. 63/352,488 filed on 6/15 of 2022, the entire contents of which are incorporated herein by reference.

Technical Field

The present disclosure relates generally to organometallic compounds and formulations and various uses thereof, including as 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 some OLED applications, phosphorescent emitters with highly homeotropic Transition Dipole Moments (TDM) are desired. For example, in plasmonic OLEDs, where high in-coupling of excited states with metal plasmonic modes yields higher efficiency, more vertical TDM emitters may be useful. A family of phosphorescent emitters designed to achieve a highly vertical TDM arrangement by molecular design is disclosed.

In one aspect, the present disclosure provides a metal coordination complex compound, wherein the metal complex compound is capable of functioning as an emitter in an OLED at room temperature, and wherein the metal complex compound has a Vertical Dipole Ratio (VDR) in the OLED of greater than 0.33.

In another aspect, the present disclosure provides a formulation comprising a metal coordination complex compound as described herein.

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

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a metal coordination complex 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.

Fig. 3 shows a graph of modeled P-polarized photoluminescence as a function of angle for emitters with different Vertical Dipole Ratio (VDR) values.

Fig. 4 shows the structure of a metal coordination complex compound as described herein, as well as its associated measurements and features.

Fig. 5 shows the structure of a metal coordination complex compound as described herein and the positions of the relevant free and bound vectors for defining plane P.

Fig. 6 shows the structure of a metal coordination complex compound as described herein and the positions of vectors W1 and W2 used to define plane P.

Fig. 7 shows the structure of a metal coordination complex compound as described herein and the position of an applicable main axis of rotation for defining plane O, as well as the Transition Dipole Moment (TDM).

Fig. 8 shows the structure of a metal coordination complex compound as described herein, as well as the needle axis and the position of TDM.

Fig. 9 shows the structure of a metal coordination complex compound as described herein and points for defining a reference plane, as well as TDM.

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 A group.

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

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

The term "phosphino" refers to-P (R _s ) 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, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-azaboron-1, 4-azaboron-nitrogen, boron-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 typical substituents are 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 general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some cases, more preferred general 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 general 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. US 2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Yan Ming (Ming Yan) et al, tetrahedron 2015,71,1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Int. Ed.) (reviewed) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacement of aromatic ring hydrogen with deuterium, respectively.

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

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

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a metal coordination complex compound, wherein the metal complex compound is capable of functioning as an emitter in an OLED at room temperature, and wherein the metal complex compound has a Vertical Dipole Ratio (VDR) in the OLED of greater than 0.33. As used herein, room temperature is about 22 ℃ (e.g., 22 ℃ ±1 ℃).

The Vertical Dipole Ratio (VDR) is the overall average fraction of dipoles in the sample oriented vertically relative to the plane of the substrate (where the vertical and normal lines of the substrate are the same). A similar concept is Horizontal Dipole Ratio (HDR), which is the ensemble average fraction of dipoles oriented horizontally relative to the substrate plane. Vdr+hdr=1 by definition. VDR can be measured by an angle dependent, polarization dependent photoluminescence measurement. By comparing the measured emission pattern of the polarization dependent optically excited film sample with a computer modeled pattern, the VDR of the emission layer can be determined. For example, modeling data for p-polarized emission is shown in fig. 3. Modeled p-polarized angular Photoluminescence (PL) was plotted for emitters with different VDRs. Peaks in the modeled PL were observed in p-polarized PL around an angle of 45 degrees, with the peak PL being larger when the VDR of the emitter is higher.

In this example for producing fig. 3, there is a 30nm thick film of material with a refractive index of 1.75, and the emission is monitored in a semi-infinite medium with a refractive index of 1.75. Each curve was normalized for photoluminescence intensity of 1 at zero degrees angle perpendicular to the film surface. As the VDR of the emitter varies, the peak around 45 degrees increases greatly. When software is used to fit the VDR of the experimental data, the modeled VDR will change until the differences between the modeled data and the experimental data are minimized.

Importantly, VDR represents the average dipole orientation of the luminescent compound. Thus, if there are additional emitters in the emissive layer that do not contribute to the emission, the VDR measurement will not report or reflect its VDR. Furthermore, by including a body that interacts with the emitters, the VDR of a given emitter can be changed, resulting in a VDR of the measured layer that is different from the VDR of the emitters in the different bodies. Furthermore, in some embodiments, it is desirable to form exciplex or excimer molecules that emit states between two adjacent molecules. These emission states may have a different VDR than the VDR when only one component in the exciplex or excimer is emitted or present in the sample.

In some embodiments, the OLED is a plasmonic OLED. In some embodiments, the OLED is a waveguide OLED.

In some embodiments, the VDR of the compound is equal to or greater than 0.4. In some embodiments, the VDR of the compound is equal to or greater than 0.5. In some embodiments, the VDR of the compound is equal to or greater than 0.6. In some embodiments, the VDR of the compound is equal to or greater than 0.7. In some embodiments, the VDR of the compound is equal to or greater than 0.8. In some embodiments, the VDR of the compound is equal to or greater than 0.9.

In a first aspect, the compound comprises a first ligand and a second ligand each coordinated to a metal.

In some embodiments of the first aspect, the second ligand is an emissive ligand. In some embodiments of the first aspect, the first ligand is a secondary ligand. As used herein, a ancillary ligand is a ligand T with a higher free ligand ₁ Ligand of energy. Free ligand T ₁ The energy may be determined by a computational procedure using Density Functional Theory (DFT) modeling. For example, DFT computation may be performed by B3LYP functional in the LACVP-based group. In the first placeIn one step, geometric optimization of the complex is performed while limiting the triplet spin density on each ligand. In a second step, the geometry is re-optimized without imposing limitations. The spin density should still be localized on the corresponding ligand. The ligands whose spin densities are localized in the lowest energy structure are considered to be emissive ligands. A ligand is considered to be the only emissive ligand if the energy difference between the ligand and the ligand of the second bit row is greater than 0.1eV or 0.20eV or 0.30 eV.

In some embodiments of the first aspect, each of the first ligand and the second ligand is a bidentate ligand.

Effective length of ligand:

in some embodiments of the first aspect, each of the first ligand and the second ligand has an effective length, and the effective length of the first ligand is at least greater than the effective length of the second ligand

In some embodiments of the first aspect, each bidentate ligand comprises ring a and ring B, wherein each of ring a and ring B coordinates to metal M and is bonded (e.g., via a direct bond) to the other of ring a and ring B. In such embodiments, each bidentate ligand has a ligand axis defined as the axis extending through the bond between ring a and ring B of the ligand.

In addition, each ligand has a ligand center defined as the bond midpoint connecting ring a and ring B. In addition, each ligand has a ligand bisector defined as an infinite line through the metal to the center of the ligand.

In addition, each ligand has a length vector defined for each atom in the ligand. Each length vector connects the relevant atom to the ligand centre. Furthermore, each ligand has values L1 and L2, where L1 is the highest value obtained in the product (magnitude of length vector) on the ring a side of the ligand bisector (cosine of the angle formed by the length vector and the ligand axis), and L2 is the highest value obtained in the product (magnitude of length vector) on the ring B side of the ligand bisector (cosine of the angle formed by the length vector and the ligand axis). In these and subsequent calculations, including measurements with molecules with the lowest total energy conformation given by geometric optimization in the ground state when part is rotatable about the axis, measurements were made using the CEP-31G basis and DFT in the B3LYP functional.

The effective length of the ligand is measured as the sum of L1 and L2 of the ligand. Examples of each of these values are shown using the chemical structure shown in fig. 4. Calculated values for L1 and L2 for the example iridium complexes in fig. 4 are shown in table 1 below.

Table 1.

The Transition Dipole Moment (TDM) may be calculated by performing a TD-DFT calculation with a Spin orbit ZORA Hamiltonian (Spin-Orbit ZORA Hamiltonian) using the B3LYP functional and the DYALL-V2Z_ZORA-J-PT-SEG basis.

In some embodiments of the first aspect, the first ligand has an effective length that is at least greater than the effective length of the second ligandIs effective length of (a). In some embodiments of the first aspect, the first ligand has an effective length at least +.>Is effective length of (a).

In some embodiments of the first aspect, the first ligand has at least 5 more non-hydrogen atoms than the second ligand. In some embodiments of the first aspect, the first ligand has at least 10 more non-hydrogen atoms than the second ligand. In some embodiments of the first aspect, the first ligand has at least 12 more non-hydrogen atoms than the second ligand.

In some embodiments of the first aspect, the first ligand has a molecular weight at least 100amu greater than the molecular weight of the second ligand. In some embodiments of the first aspect, the first ligand has a molecular weight at least 150amu greater than the molecular weight of the second ligand. In some embodiments of the first aspect, the first ligand has a molecular weight at least 200amu greater than the molecular weight of the second ligand.

In some embodiments of the first aspect, the first ligand has at least 3 more aliphatic methylene carbons (e.g., CH ₂ ). In some embodiments of the first aspect, the first ligand has at least 5 more aliphatic methylene carbons than the second ligand. In some embodiments of the first aspect, the first ligand has at least 8 more aliphatic methylene carbons than the second ligand.

In some embodiments of the first aspect, the compound comprises a tetradentate ligand formed from one of the first ligand and the second ligand or from the first ligand conjugated to the second ligand. In some embodiments of the first aspect, the first ligand and the second ligand join to form a tetradentate ligand.

In some embodiments of the first aspect, the difference in the number of R moieties between the first ligand and the second ligand is at least two. In some embodiments of the first aspect, the difference in the number of R moieties between the first ligand and the second ligand is at least three. In some embodiments of the first aspect, the difference in the number of R moieties between the first ligand and the second ligand is at least four.

In some embodiments of the first aspect, the first ligand comprises at least two more R moieties than the second ligand. In some embodiments, the second ligand comprises at least two more R moieties than the first ligand.

As used herein, each R moiety is independently a substituent selected from the group consisting of: 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, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In some embodiments, each R moiety is independently selected from the group consisting of: halogen, CF ₃ 、CN、FC=o and OR ^w Wherein each R is ^w Independently selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In some embodiments of the first aspect, wherein the metal M has an atomic weight greater than 40. In some such embodiments, the metal M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au and Cu. In some such embodiments, the metal M is Ir or Pt. In some such embodiments, the metal M is Pt.

In some embodiments of the first aspect, the complex compound further comprises a third ligand.

In some embodiments of the first aspect, the first ligand and the third ligand are the same. In some embodiments of the first aspect, the second ligand and the third ligand are the same.

In some embodiments of the first aspect, the first ligand and the third ligand are the same ancillary ligand, and the second ligand is an emissive ligand. In some embodiments of the first aspect, the first ligand and the third ligand are different ancillary ligands, and the second ligand is an emissive ligand. In some embodiments of the first aspect, the second ligand and the third ligand are the same emissive ligand and the first ligand is a helper ligand.

In some embodiments of the first aspect, the compound has the formula M (L _A ) _x (L _B ) _y (L _C ) _z ；

Wherein L is _A 、L _B And L _C 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 _A Selected from the group consisting of:

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wherein L is _B And L _C Independently selected from the group consisting of: />

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

wherein E is selected from the group consisting of: o, S, se and Te;

Wherein K is ¹ ' is a direct bond or is selected from the group consisting of: NR (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: BR (BR) _e 、NR _e 、PR _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f ；

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

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

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 as 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 adjacent substituents of (a) may be fused or joined to form a ring or to form a multidentate ligand.

In some embodiments of the above compounds, R _a 、R _b Or R is _c Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, R _a 、R _b Or R is _c One of which is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, R _a 、R _b Or R is _c One of which is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, R _a 、R _b Or R is _c One of which is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, R _a 、R _b Or R is _c One of which is an electron withdrawing group from a list Pi-EWG as defined herein.

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

/>

wherein:

R ₁ 、R _1' 、R ₂ and R is _2' Independently represents a single substitution to a maximum number of permissible substitutions, or no substitution;

each R ₁ 、R _1' 、R ₂ 、R _2' 、R ₃ And R is _3' Independently hydrogen or a substituent 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, sulfinyl, sulfonyl, phosphino, borane, seleno, and combinations thereof; and is also provided with

Any two R ₁ 、R _1' 、R ₂ 、R _2' 、R ₃ Or R is _3' May be joined or fused to form a ring.

In some embodiments of the above compounds, R ₁ 、R _1' 、R ₂ Or R is _2' Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, R ₁ 、R _1' 、R ₂ Or R is _2' One of which is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, R ₁ 、R _1' 、R ₂ Or R is _2' One of them is from the originList EWG 3 as defined herein. In some embodiments of the compounds, R ₁ 、R _1' 、R ₂ Or R is _2' One of which is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, R ₁ 、R _1' 、R ₂ Or R is _2' One of which is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the first aspect, the one or more ligands are independently selected from the group consisting of:

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wherein the variables are the same as previously defined.

In some of the above embodiments, Y ¹ Or Y ² Is substituted.

In some embodiments of the first aspect, the one or more emissive ligands are independently selected from the group consisting of:

therein E, R ₁ 、R ₂ And R is ₃ As defined previously.

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

/>

wherein:

X ⁹⁶ to X ⁹⁹ Is independently C or N;

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

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

each R ^10a 、R ^20a 、R ^30a 、R ^40a And R is ^50a Independently represents mono-substitution up to maximum 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 and R is ⁹⁹ Is 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.

In some embodiments of the above compounds, R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a One of which is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a One of which is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a One of which is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a One of which is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, the compound has the formula M (L _A )(L _B )(L _C ). In some such embodiments, L _B And L _C Are linked by a linker to form a tetradentate ligand. In some such embodiments, the linker may be a 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.

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

/>

and partially and fully deuterated variants thereof.

In a second aspect, the compound comprises at least two ligands coordinated to the metal M; wherein the complex compound has a first free vector F ₁ Consisting of a ring connecting any two atoms in the compound and being of the metalInner transfer and with a content of more than->First constraint vector M of length of (2) ₁ A representation; wherein the said compound The object has a second free vector F ₂ Consisting of a linkage of any two atoms in said compound and having a weight greater than +.>Second constraint vector M of length of (2) ₂ A representation; and wherein the transmission transition dipole moment vector and vector F ₁ And F ₂ The angle between the cross-products is less than 45 degrees.

In some embodiments of the second aspect, a second vector F ₂ And F is equal to ₁ Forming an angle greater than 45 degrees.

In more than one pair of atoms, the atoms conform to a pair first constraint vector M ₁ In the case of requirements of (2), the pair forming the longest first bounding vector meeting other requirements is selected. In which more than one pair of atoms corresponds to a second constraint vector M ₂ In the case of a requirement of (2), the pair forming the longest second bounding vector meeting other requirements is selected.

In some embodiments of the second aspect, the complex compound has a first free vector F ₁ Consisting of a ring connecting any two atoms in the compound and being of the metalInner transfer and with a content of more than->First constraint vector M of length of (2) ₁ A representation; wherein the compound has a second free vector F ₂ Consisting of a linkage of any two atoms in said compound and having a weight greater than +.>Second constraint vector M of length of (2) ₂ A representation; and wherein the transmission transition dipole moment vector and vector F ₁ And F ₂ The angle between the cross-products is less than 45 degrees. />

In some embodiments of the second aspect, a second bounding vector M is formed ₂ Is in the same ligand and is shapedFirst constraint vector M ₁ Is in a different ligand. In some embodiments of the second aspect, a second bounding vector M is formed ₂ The atoms forming a first binding vector M ₁ Any of the different ligands in the atom of (c).

For compoundsAn example is shown in fig. 5. As defined herein, the vector defined by two points in space in the reference frame of the compound is referred to as the "binding vector" (e.g., M1 and M2). The position of the binding vector in space in the reference frame of the compound is fixed at the particular position within the reference frame of the compound. In contrast, a "free vector" like F1 or F2 has only magnitude and direction. In this case, plane P is defined by free vectors F1 and F2 and metal M. Thus, the cross product of F1 and F2 will define the normal to plane P.

Sample calculations for the compounds in fig. 5 are provided in table 2 below:

in this aspect, the coordinates of the atoms are determined using the lowest energy structure in the triplet state, where the spin is limited to the emission ligands using the LACVP-based group and DFT in the B3LYP functional. This geometry is then used to calculate the Transition Dipole Moment (TDM).

In Table 2, "maximum-t distance from plane P"means the maximum perpendicular distance of an atom from plane P.

In some embodiments of the second aspect, at least two ligands are bidentate ligands.

In some embodiments of the second aspect, the complex compound comprises three bidentate ligands coordinated to metal M. In some such embodiments, each of the three bidentate ligands is different.

In some embodiments of the second aspect, a second vector F ₂ Is a linker linking any two atoms in the molecule and to F ₁ Forming the longest vector of an angle greater than 60 degrees.

In some embodiments of the second aspect, F ₁ And F ₂ Are all longer thanIn some embodiments of the second aspect, F ₁ And F ₂ Is greater than +.>

In some embodiments of the second aspect, the transition dipole moment vector and vector F are launched ₁ And F ₂ The angle between the cross-products is less than 30 degrees. In some embodiments of the second aspect, the transition dipole moment vector and vector F are launched ₁ And F ₂ The angle between the cross-products is less than 20 degrees.

In some embodiments of the second aspect, the compound has a vector defined by the free vector F ₁ And F ₂ A defined plane P, said free vectors being defined by corresponding constraint vectors M ₁ And M ₂ Represented, and plane P is parallel to M ₁ And M ₂ And passes through the metal M; and the sum of the vertical distance from plane P to the most distant atom above plane P and the vertical distance from plane P to the most distant atom below plane P is smaller thanIn some such embodiments, the sum of the perpendicular distance from plane P to the most distant atom above plane P and the perpendicular distance from plane P to the most distant atom below plane P is less than +.> In some such embodiments, the sum of the perpendicular distance from plane P to the most distant atom above plane P and the perpendicular distance from plane P to the most distant atom below plane P is less than +.>/>

For the distance of the point from the plane, the perpendicular distance from the plane P is calculated using a standard formula:

wherein a, b, c are components of a plane normal vector, x ₀ 、y ₀ 、z ₀ Is the coordinates of the atoms, and d is a constant of the plane equation that ensures that the plane passes through the metal atoms.

In some embodiments of the second aspect, the metal M has an atomic weight greater than 40. In some embodiments of the second aspect, the metal M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au and Cu. In some embodiments of the second aspect, the metal M is Ir.

In some embodiments of the second aspect, the compound may have the formula M (L _A ) _x (L _B ) _y (L _C ) _z . In some embodiments of the second aspect, the compound may have the formula M (L _A )(L _B )(L _C ) Wherein the variables are the same as previously defined. It will be appreciated that those compounds of the first aspect may be similarly applicable herein, provided that the conditions of the second aspect are met.

In some embodiments of the second aspect, the complex compound has the following structure:

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wherein:

R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' and R is _2#" Independently represents a single substitution to the maximum allowable substitution, or no substitution;

each R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' 、R _2#"' And R is _3# Independently hydrogen or a substituent 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, sulfinyl, sulfonyl, phosphino, borane, seleno, and combinations thereof; and is also provided with

Any two R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' And R is _2#" May be joined or fused to form a ring; and is also provided with

Each E' is independently S or O.

In some embodiments of the second aspect, the second free vector is defined by R _2# One atom and R _1# Is formed by one atom of (a) and a first free vector is formed by R _1#' One atom and R _2#" Is formed by one atom of the group.

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

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in a third aspect, the compound has at least two ligands that coordinate to the metal M; wherein the compound has two metal coordination bonds in the trans configuration; wherein the compound has a first vector W formed between any atom on the periphery of the compound and the metal ₁ The method comprises the steps of carrying out a first treatment on the surface of the Wherein the compound has a second vector W formed between any other atom on the periphery of the compound and the metal ₂ The method comprises the steps of carrying out a first treatment on the surface of the Wherein W is ₁ And W is ₂ Is greater in magnitude than each ofAnd wherein the transmission transition dipole moment vector and vector W ₁ And W is ₂ The angle between the cross-products is less than 45 degrees. In some embodiments of the third aspect, the first vector W having the largest possible value is selected ₁ And a second vector W ₂ 。

For the followingAn example of such an arrangement is shown in fig. 6. As used herein, atoms on the periphery refer to atoms in the moiety furthest from the metal M and not masked by other atoms. In the structure of fig. 6, the furthest atom on the periphery refers to the terminal H atom in the cyclohexane 4-position.

Sample calculations for the compounds in fig. 6 are provided in table 3 below:

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in this aspect, there may be no unique emissive ligand defined by the criteria described herein. In this aspect, the atomic coordinates from the lowest energy structure are used. In the case of two structures with spin densities on two separate ligands and the same energy, atomic coordinates from either structure may be used. The structure is then used to calculate a Transition Dipole Moment (TDM).

In some embodiments, W ₁ Measured using two atoms from the periphery of the first ligand, and W ₂ Measured using two atoms from the periphery of a second ligand different from the first ligand.

In some embodiments of the third aspect, W ₁ And W is ₂ Each of which is larger thanIn some embodiments of the third aspect, W ₁ And W is ₂ Is greater than +.>

In some embodiments of the third aspect, the transition dipole moment vector and vector W are transmitted ₁ And W is ₂ The angle between the cross-products is less than 30 degrees. In some embodiments of the third aspect, the transition dipole moment vector and vector W are transmitted ₁ And W is ₂ The angle between the cross-products is less than 20 degrees.

In some embodiments of the third aspect, the compound has a vector W ₁ And W is ₂ Define and parallel to vector W ₁ And W is ₂ Plane P of (2); and the sum of the vertical distance from plane P to the most distant atom above plane P and the vertical distance from plane P to the most distant atom below plane P is smaller thanIn some embodiments of the third aspect, the sum of the perpendicular distance from plane P to the atom furthest above plane P and the perpendicular distance from plane P to the atom furthest below plane P is less than +.>In some embodiments of the third aspect, the sum of the perpendicular distance from plane P to the atom furthest above plane P and the perpendicular distance from plane P to the atom furthest below plane P is less than +.>

In some embodiments of the third aspect, the angle between the metal coordination bond and the Transition Dipole Moment (TDM) vector is less than 30 degrees. In some embodiments of the third aspect, the angle between the metal coordination bond and the Transition Dipole Moment (TDM) vector is less than 20 degrees. In some embodiments of the third aspect, the angle between the metal coordination bond and the Transition Dipole Moment (TDM) vector is less than 10 degrees.

In some embodiments of the third aspect, the metal M has an atomic weight greater than 40. In some embodiments of the third aspect, the metal M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au and Cu. In some embodiments of the third aspect, the metal M is Ir.

In some embodiments of the third aspect, the compound may have the formula M (L _A ) _x (L _B ) _y (L _C ) _z . In some embodiments of the third aspect, the compound may have the formula M (L _A )(L _B )(L _C ) Wherein the variables are the same as previously defined. It will be appreciated that those compounds of the first or second aspects may be similarly applicable herein, provided that the conditions of the third aspect are met.

In some embodiments of the third aspect, the compound has Ir (L _A ) _m (L _B ) _3-m Is of a structure of (2);

wherein L is _A And L _B Each independently is a bidentate ligand;

wherein m=1 or 2;

wherein L is _A Has a structure selected from the group consisting of:/>

wherein L is _A Coordination to Ir by the dashed line;

wherein R is _1* And R is _B* Independently mono-substituted up to a maximum number of possible substitutions, or no substitution;

wherein each R is _1* Independently hydrogen or a substituent selected from the group consisting of: alkyl, partially or fully deuterated alkyl, nitrile, ether, halogen, and combinations thereof;

wherein E' is independently selected from O or S;

wherein R is _2* Is a 5-or 6-membered carbocyclic or heterocyclic ring substituted with a substituent selected from the group consisting of: alkyl groups having greater than 2 carbon atoms, cycloalkyl groups, aryl groups, heteroaryl groups, nitriles, ethers, halogens and combinations thereof;

Wherein each R is _B* And R is _3* Independently hydrogen or a substituent selected from the group consisting of the universal substituents defined herein; and is also provided with

Wherein any two R' s _1* Or R is _B* May be joined or fused together to form a ring.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), any two adjacent R' s _1* Or R is _B* May be joined or fused together to form a ring.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structures of (2), ring B is an aryl or heteroaryl ring. In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), ring B is a 5-membered ring.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), at least one R _1* Not hydrogen.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), R _2* Is a 5-or 6-membered carbocyclic or heterocyclic ring which is substituted by cycloalkylA substituent of at least one of aryl or heteroaryl. In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), R _2* Is a 5-or 6-membered aliphatic ring substituted with a substituent selected from the group consisting of: alkyl groups having greater than 2 carbon atoms, cycloalkyl groups, aryl groups, heteroaryl groups, nitriles, ethers, halogens, and combinations thereof. In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), R _2* Is a 5-or 6-membered aromatic ring substituted with a substituent selected from the group consisting of: alkyl groups having greater than 2 carbon atoms, cycloalkyl groups, aryl groups, heteroaryl groups, nitriles, ethers, halogens, and combinations thereof.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), L _B The structure is as follows: a formula II, Wherein R is ₃ 、R ₄ 、R ₅ 、R ₆ And R is ₇ Independently hydrogen or a substituent selected from the group consisting of the generic substituents defined herein.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), two adjacent R' s _B Joined or fused together to form a ring. In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), two adjacent R' s _B Joined to form a benzyl ring.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), m is 1. In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (2), m is 2.

In the presence of Ir (L) _A ) _m (L _B ) _3-m In some embodiments of the structure of (a),L _A selected from the group consisting of:

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in some embodiments of the third aspect, the compound hasWherein the virtual ring may be a 5-or 6-membered heterocyclic or carbocyclic ring, which may be substituted with one or more of the general substituents defined herein. In some such embodiments, the virtual wire ring may be a 5-membered ring. In some such embodiments, the virtual wire ring may be a 6-membered ring. In some such embodiments, the virtual wire loop may be aromatic. In some such embodiments, the virtual wire ring may be a benzyl ring.

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

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in a fourth aspect, the compound defines a parameter D and a plane O through the metal M, wherein the plane O is formed by a main axis of rotation 1 and a main axis of rotation 2, the main axis of rotation being the main axis of rotation with the smallest main moment of inertia. In the compound, the calculated angle between the normal vector relative to plane O and the Transition Dipole Moment (TDM) vector is less than 45 degrees; and parameter D is greater than 0.4. Parameters (parameters)Wherein I is ₁ 、I ₂ And I ₃ Is the dominant moment of inertia of the complex compound.

This relates to compoundsAn example of (c) is shown in figure 7. The main moment of inertia and the main axis of rotation are obtained from the angular momentum of the molecules in the following manner:

the angular momentum of a molecule in the XYZ coordinate system is defined as:

wherein m is _i Is mass, and x _i 、y _i And z _i Is the x, y and z coordinates of atom i, and ω is the angular velocity.

Factorization I: i=qΛq ^T

Wherein:

and I ₁ 、I ₂ And I ₃ Is the main moment of inertia, the Q column is the main axis of rotation, and Q ^T Is a transpose of Q. As will be appreciated, these values can be obtained using a variety of software packages, such as Schrodinger's Maestro. Given two axis vectors, the normal to the plane it spans can be defined as its cross product. After this, the angle between the TDM vector and normal can be calculated. The angle is subtracted from 90 degrees and the angle between TDM and plane is obtained. The calculations are based on the configuration of the compound at the lowest energy state.

A calculated example for the compound of fig. 7 is shown in table 4 below:

I ₁	I ₂	I ₃	D	angle (degree) between TDM and plane O normal
					12487	19402	23794	0.45	13

The data in table 4 were obtained using the lowest energy state configuration described herein. A Transition Dipole Moment (TDM) is calculated from the structure.

In some embodiments of the fourth aspect, the calculated angle between the normal vector relative to plane O and the Transition Dipole Moment (TDM) vector is less than 30 degrees. In some embodiments of the fourth aspect, the calculated angle between the normal vector relative to plane O and the Transition Dipole Moment (TDM) vector is less than 20 degrees.

In some embodiments of the fourth aspect, D is greater than 0.5. In some embodiments of the fourth aspect, D is greater than 0.6. In some embodiments of the fourth aspect, D is greater than 0.7.

In some embodiments of the fourth aspect, the metal M has an atomic weight greater than 40. In some embodiments of the fourth aspect, the metal M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, au and Cu. In some embodiments of the fourth aspect, the metal M is Ir.

In some embodiments of the fourth aspect, the compound may have the formula M (L _A ) _x (L _B ) _y (L _C ) _z . In some embodiments of the fourth aspect, the The compound may have the formula M (L _A )(L _B )(L _C ) Wherein the variables are the same as previously defined. It will be appreciated that those compounds of the first, second or third aspects may be similarly applicable herein provided that the conditions of the fourth aspect are met.

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

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in a fifth aspect, the compound is a four-coordinate square planar complex having an axis K corresponding to the main axis of rotation with minimal main moment of inertia and a rod-like parameter R ^R The method comprises the steps of carrying out a first treatment on the surface of the Wherein the calculated angle between the rod axis and the transition dipole moment vector is greater than 45 degrees; wherein the method comprises the steps ofAnd I ₁ 、I ₂ And I ₃ Is the dominant moment of inertia; and wherein R is ^R Greater than 0.6.

Examples are described with respect to the compounds in fig. 8. The main rotation axis is to be understood as the rotation axis having the smallest main moment of inertia. The main moment of inertia (I) can be calculated using the Schrodinger's Maestro program group ₁ 、I ₂ And I ₃ ) A rod-like axis (e.g., axis K). Calculating the parameters R from the three main moments of inertia using the above formula ^R . The lowest energy state configuration was used for calculation. Example calculations for the compounds of fig. 7 are shown in table 5 below:

I ₁	I ₂	I ₃	R ^R	angle (degree) between TDM and rod-like axis
					6611	16210	21713	0.47	46

The data in table 5 were obtained using the lowest energy state configuration described herein. A Transition Dipole Moment (TDM) is calculated from the structure.

In some embodiments of the fifth aspect, the calculated angle between the rod axis and the Transition Dipole Moment (TDM) vector is greater than 60 degrees. In some embodiments of the fifth aspect, the calculated angle between the rod axis and the Transition Dipole Moment (TDM) vector is greater than 75 degrees.

In some embodiments of the fifth aspect, R ^R Greater than 0.7. In some embodiments of the fifth aspect, R ^R Greater than 0.8.

In some embodiments of the fifth aspect, the metal M is selected from the group consisting of: pt, pd, ag and Cu. In some embodiments of the fifth aspect, the metal is Pt or Pd.

In some embodiments of the fifth aspect, the complex compound has the formula M (L _A )(L _B ) Wherein L is _A And L _B As previously defined, and L _A And L _B May be joined to form a tetradentate ligand.

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

/>

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

l is independently selected from the group consisting of: no bond, 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;

each R ^A″ 、R ^B″ 、R ^C″ 、R ^D″ 、R ^E″ And R is ^F″ Independently represents mono-substitution up to maximum 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.

In some embodiments of the fifth aspect, the complex compound hasIn which

R _1a And R is _2a Independently represents a single substitution to the maximum allowable substitution, or no substitution;

each R _1a 、R _2a 、R _1a' 、R _2a' And R is _3a' Independently hydrogen or a substituent selected from the group consisting of the universal substituents defined herein; and is also provided with

Any two R _1a 、R _2a 、R _1a' 、R _2a' And R is _3a' Can be joined or fused to formForming a ring.

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

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in a sixth aspect, the compound is a four-coordinate square planar complex in which the transition dipole moment deviates from a reference plane defined by at least three atoms at the periphery of the ligand by not less than 45 degrees, the at least three atoms being at least apart from each other

In some embodiments of the sixth aspect, only one ligand may be present and spin localization steps in the geometry optimization procedure are not necessary. Atomic coordinates are then obtained from the lowest geometry in the triplet state. This geometry is used to calculate the Transition Dipole Moment (TDM).

An example of such an arrangement and reference plane is shown in fig. 9. In some embodiments, as in the embodiment of fig. 9, the ligand comprises a first ring and a second ring bonded to each other and each coordinated to the metal M, wherein one of the at least three atoms is part of a substituent bonded to the first ring (e.g., a benzene ring fused to an imidazole), and two of the at least three atoms are part of a substituent bonded to the second ring (e.g., an M-terphenyl). In some embodiments, the substituents are combined to form a long axis or plane oriented at an angle (θ in fig. 9) greater than 60, 70, or 80 degrees relative to the emitter TDM vector.

As will be appreciated, the moiety such as m-terphenyl may rotate together about the second ring (benzene). As explained herein, for the purpose of determining the position of the reference plane, it is assumed that m-terphenyl is in the lowest energy state.

In some embodiments of the sixth aspect, the calculated angle between the reference plane and the Transition Dipole Moment (TDM) vector is greater than 60 degrees. In some embodiments of the sixth aspect, the calculated angle between the reference plane and the Transition Dipole Moment (TDM) vector is greater than 75 degrees.

In some embodiments of the sixth aspect, the metal M is selected from the group consisting of: pt, pd, ag and Cu. In some embodiments of the sixth aspect, the metal M is Pt or Pd.

In some embodiments of the sixth aspect, the complex compound has the formula M (L _A )(L _B ) Wherein L is _A And L _B As previously defined, and L _A And L _B May be joined to form a tetradentate ligand. Those compounds of the fifth aspect may be similarly applied to the sixth aspect as long as those compounds also meet the conditions of the sixth aspect.

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

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throughout this disclosure, formula M (L _A ) _x (L _B ) _y (L _C ) _z May comprise one or more electron withdrawing groups.

In some embodiments of the compounds, at least L _A Comprising electron withdrawing groups from the list EWG 1 as defined herein. In some embodiments of the compounds, at least L _A Comprising electron withdrawing groups from the list EWG 2 as defined herein. In some embodiments of the compounds, at least L _A Comprising electron withdrawing groups from the list EWG 3 as defined herein. In some embodiments of the compounds, at least L _A Comprising electron withdrawing groups from the list EWG 4 as defined herein. In some embodiments of the compounds, at least L _A Comprising electron withdrawing groups from a list Pi-EWG as defined herein.

In some embodiments of the compounds, at least L _B Comprising electron withdrawing groups from the list EWG 1 as defined herein. In some embodiments of the compounds, at least L _B Comprising electron withdrawing groups from the list EWG 2 as defined herein. In some embodiments of the compounds, at least L _B Comprising electron withdrawing groups from the list EWG 3 as defined herein. In some embodiments of the compounds, at least L _B Comprising electron withdrawing groups from the list EWG 4 as defined herein. In some embodiments of the compounds, at least L _B Comprising electron withdrawing groups from a list Pi-EWG as defined herein.

In some embodiments of the compounds, at least L _C Comprising electron withdrawing groups from the list EWG 1 as defined herein. In some embodiments of the compounds, at least L _C Comprising electron withdrawing groups from the list EWG 2 as defined herein. In some embodiments of the compounds, at least L _C Comprising electron withdrawing groups from the list EWG 3 as defined herein. In some embodiments of the compounds, at least L _C Comprising electron withdrawing groups from the list EWG 4 as defined herein. In some embodiments of the compounds, at least L _C Comprising electron withdrawing groups from a list Pi-EWG as defined herein.

In some embodiments, the electron withdrawing group generally comprises one or more highly electronegative elements including, but not limited to, fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.

In some embodiments of the compounds, the electron withdrawing group has a Hammett constant (Hammett constant) greater than 0. In some embodiments, the Hammett constant of the electron withdrawing group is equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

In some embodiments, the electron withdrawing group is selected from the group consisting of the following structures (list EWG 1): F. CF (compact flash) ₃ 、CN、COCH ₃ 、CHO、COCF ₃ 、COOMe、COOCF ₃ 、NO ₂ 、SF ₃ 、SiF ₃ 、PF ₄ 、SF ₅ 、OCF ₃ 、SCF ₃ 、SeCF ₃ 、SOCF ₃ 、SeOCF ₃ 、SO ₂ F、SO ₂ CF ₃ 、SeO ₂ CF ₃ 、OSeO ₂ CF ₃ 、OCN、SCN、SeCN、NC、 ⁺ N(R ^k2 ) ₃ 、(R ^k2 ) ₂ CCN、(R ^k2 ) ₂ CCF ₃ 、CNC(CF ₃ ) ₂ 、BR ^k3 R ^k2 Substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, />

Wherein Y is ^G Selected from the group consisting of: BR (BR) _e 、NR _e 、PR _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f' The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

R ^k1 Each independently represents a single substitution to the maximum allowable substitution, or no substitution;

wherein R is ^k1 、R ^k2 、R ^k3 、R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of the generic substituents defined herein.

In some embodiments, the electron withdrawing group is selected from the group consisting of the following structures (list EWG 2):

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in some embodiments, the electron withdrawing group is selected from the group consisting of the following structures (list EWG 3):

in some embodiments, the electron withdrawing group is selected from the group consisting of the following structures (list EWG 4):

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in some embodiments, the electron withdrawing group is a pi-electron deficient electron withdrawing group. In some embodiments, the Pi-electron deficient electron withdrawing group is selected from the group consisting of the following structures (list Pi-EWG): CN, COCH ₃ 、CHO、COCF ₃ 、COOMe、COOCF ₃ 、NO ₂ 、SF ₃ 、SiF ₃ 、PF ₄ 、SF ₅ 、OCF ₃ 、SCF ₃ 、SeCF ₃ 、SOCF ₃ 、SeOCF ₃ 、SO ₂ F、SO ₂ CF ₃ 、SeO ₂ CF ₃ 、OSeO ₂ CF ₃ 、OCN、SCN、SeCN、NC、 ⁺ N(R ^k1 ) ₃ 、BR ^k1 R ^k2 Substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially fluorinated and perfluorinated aryl, partially fluorinated and perfluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

Wherein the variables are the same as previously defined.

In some embodiments of the sixth aspect, the compound comprises at least one deuterium atom.

In some embodiments of the sixth aspect, the compound comprises at least 10 deuterium atoms.

In some embodiments, the metal coordination complex compounds described herein may be at least 10% deuterated, at least 20% deuterated, 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, deuteration percentage has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., hydrogen or deuterium sites) replaced by deuterium atoms.

C. OLED and device of the present disclosure

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

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

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

In some embodiments, the organic layer is at least 10% deuterated. In some embodiments, at least one compound is at least 10% deuterated. In some embodiments, each compound in the organic layer is at least 10% deuterated.

In some embodiments, the organic layer is at least 50% deuterated. In some embodiments, at least one compound is at least 50% deuterated. In some embodiments, each compound in the organic layer is at least 50% deuterated.

In some embodiments, the organic layer is at least 90% deuterated. In some embodiments, at least one compound is at least 90% deuterated. In some embodiments, each compound in the organic layer is at least 90% deuterated.

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, 5λ2-benzo [ d ] benzo [3,2-a ] imidazole, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-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: no bond, O, S, se, CRR ', siRR', geRR ', NR, BR, BRR';

R ^A' 、R ^B' 、R ^C' 、R ^D' 、R ^E' 、R ^F' and R is ^G' Independently represents mono-substitution up to maximum substitution, or no substitution;

Each R, R ^' 、R ^A' 、R ^B' 、R ^C' 、R ^D' 、R ^E' 、R ^F' And R is ^G' Independently 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;

R ^A' 、R ^B' 、R ^C' 、R ^D' 、R ^E' 、R ^F' and R is ^G' 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, 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 metal coordination complex 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 effect of the medium as a whole 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 a metal coordination complex compound as described herein.

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

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

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

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

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

Fig. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. 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 1:1 molar ratio, 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 present disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation may comprise one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

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

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

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

a) Conductive dopants:

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

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

b)HIL/HTL：

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

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

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

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

wherein k is an integer 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 With phases as defined aboveAn homogroup.

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, benzothiophene pyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

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

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

E. Experimental data

For determination of VDR, the VDR was determined by vacuum thermal evaporation on a UV ozone pretreated glass substrateIs then +.>Is doped with 3% -5% of an emitter of compound H1 or compound H3 to produce a film for angle dependent photoluminescence. Photoluminescence related to the polarization angle was then measured using a Fluxim Phelos system with 340nm or 405nm excitation source and fitted with Setfos software to give VDR. The Phelos spectral intensity versus angle is obtained by integrating the wavelength regime over a range that excludes excitation source scattering.

The fitting routine within Setfos is as follows. The optical stack was set to be identical to the experiment with a 0.7mm glass substrate measuring emission, a 40nm EML film with emitter, and air as the final term. The emitter distribution was exponentially set, with its position at the top air-EML interface and width of 50nm. The integrated p-and s-polarized spectral intensities versus angle are used as input targets for the Setfos fitting/optimization routine. The optimized fitting parameters are as follows: emitter orientation (VDR), emission intensity, and EML refractive index. The VDR resulting from this fit is the reported value, where VDR = vertical dipole ratio (0.33 is random, any value less than 0.33 is flat aligned).

TABLE 6

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Wherein E1-29 and H1-3 have the following structures:

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these experimental VDR results in table 6 represent the criteria required herein to achieve >0.33VDR complex, compared to the Comparative Example (CE) listed in the table.

Claims

1. A metal coordination complex compound, wherein the compound is capable of functioning as an emitter in an organic light emitting device, OLED, at room temperature, and wherein the compound has a vertical dipole ratio, VDR, in the OLED of greater than 0.33.

2. The compound of claim 1, wherein the compound comprises a first ligand and a second ligand each coordinated to a metal; and/or

Wherein each ligand has an effective length, and wherein the effective length of the first ligand is at least greater than the effective length of the second ligandAnd/or

Wherein the first ligand has at least 5 more non-hydrogen atoms than the second ligand; and/or

Wherein the first ligand has a molecular weight at least 100amu greater than the molecular weight of the second ligand; and/or

Wherein the first ligand has at least 3 more aliphatic methylene carbons than the second ligand.

3. The compound of claim 2, wherein the difference in the number of R moieties between the first ligand and the second ligand is at least two; and is also provided with

Wherein each R moiety is independently selected from the group consisting of: halogen, CF ₃ CN, F, c=o and OR ^w ；

Wherein each R is ^w Independently selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof.

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

5. The compound of claim 2, wherein the compound is selected from the group consisting of:

wherein:

R ₁ 、R _1' 、R ₂ and R is _2' Independently represents a single substitution to the maximum allowable substitution, or no substitution;

6. The compound of claim 2, wherein the compound is selected from the group consisting of:

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7. the compound of claim 1, wherein the compound comprises at least two ligands coordinated to metal M; wherein the compound has a first free vector F ₁ Consisting of a ring connecting any two atoms in the compound and being of the metalInternal passing constraint vector M ₁ Represents, and M ₁ Is greater than +.>Wherein the compound has a second free vector F ₂ Which consists of a binding vector M linking any two atoms in the compound ₂ A representation; and M is ₂ Is longer than (1)And wherein the transmission transition dipole moment vector and vector F ₁ And F ₂ The angle between the cross-products is less than 45 degrees.

8. The compound of claim 7, wherein the compound has the structure:

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wherein:

R、R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' 、R _2#" and R is _3# Independently represents a single substitution to the maximum allowable substitution, or no substitution;

each R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' 、R _2#" And R is _3# Independently hydrogen or a substituent 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, sulfinyl, sulfonyl, phosphino, borane, seleno, and combinations thereof;

Each E' is independently S or O; and is also provided with

Any two R _1# 、R _1#' 、R _1#" 、R _2# 、R _2#' And R is _2#" May be joined or fused to form a ring.

9. The compound of claim 1, wherein the compound has at least two ligands coordinated to metal M;

wherein the compound has two metal coordination bonds in the trans configuration;

wherein the compound has a first vector W formed between any atom on the periphery of the compound and the metal ₁ ；

Wherein the compound has a second vector W formed between any other atom on the periphery of the compound and the metal ₂ The method comprises the steps of carrying out a first treatment on the surface of the Wherein W is ₁ And W is ₂ Each magnitude of (2) is greater thanAnd->

Wherein the transmission transition dipole moment vector and vector W ₁ And W is ₂ The angle between the cross-products is less than 45 degrees.

10. The compound according to claim 9, wherein the compound has Ir (L _A ) _m (L _B ) _3-m Is of a structure of (2);

wherein L is _A And L _B Each independently is a bidentate ligand;

wherein m=1 or 2;

wherein L is _A Has a structure selected from the group consisting of:

wherein L is _A Coordination to Ir by the dashed line;

Wherein E' is independently selected from O or S;

wherein each R is _B* And R is _3* Independently hydrogen or a substituent 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, sulfinyl, sulfonyl, phosphino, borane, seleno, and combinations thereof; and is also provided with

11. The compound of claim 9, wherein L _B The structure is as follows: a formula II,

Wherein R is ₃ 、R ₄ 、R ₅ 、R ₆ And R is ₇ Is independently hydrogen or a substituent 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, sulfinyl, sulfonyl, phosphino, borane, seleno, and combinations thereof.

12. The compound of claim 1, comprising a parameter D and a plane O, wherein plane O is defined as the plane formed by the main axis of rotation 1 and the main axis of rotation 2 through the metal M, the main axis of rotation being the main axis of rotation with the smallest main moment of inertia;

wherein the method comprises the steps ofWherein I is ₁ 、I ₂ And I ₃ Is the dominant moment of inertia of the compound;

wherein the calculated angle between the normal vector relative to plane O and the transition dipole moment TDM vector is less than 45 degrees; and is also provided with

Wherein D is greater than 0.4.

13. The compound of claim 1, wherein the compound is a four-coordinate square plane having an axis K corresponding to the main axis of rotation with minimal main moment of inertia and a stick parameter R calculated from the three main moments of inertia of the compound ^R ；

Wherein the calculated angle between the rod axis and the transition dipole moment vector is greater than 45 degrees; and is also provided with

Wherein R is ^R Greater than 0.6; or (b)

Wherein the compound is a four-coordinate square plane in which the transition dipole moment deviates from a reference plane defined by at least three atoms at the periphery of the ligand by not less than 45 degrees, the at least three atoms being at least apart from each other

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 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