KR20210131897A - Organic electroluminescent materials and devices - Google Patents

Abstract

Provided is a transition metal compound having 1,2,3-triazine. In addition, provided is a compound comprising the transition metal compounds having 1,2,3-triazine. Further, provided are an OLED and a related consumer product utilizing the transition metal compounds having 1,2,3-triazines.

Description

ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is filed under 35 U.S.C. Priority is claimed to U.S. Provisional Application No. 63/013,930, filed on April 22, 2020 under § 119(e), the entire contents of which are incorporated herein by reference.

Field

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

Optoelectronic devices using organic materials are becoming increasingly important for several reasons. Because many of the materials used to make such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the intrinsic properties of organic materials, such as their flexibility, may make them well suited for certain 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 use thin organic films that emit light when a voltage is applied to the device. OLEDs are an increasingly important technology for use in applications such as flat panel displays, lighting and backlighting.

One application for phosphorescent emitting molecules is full color displays. The industry standard for such displays requires pixels tuned to emit a specific color, referred to as a “saturated” color. In particular, this criterion requires saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In a typical liquid crystal display, light emission from a white backlight is filtered using an absorption filter to produce red, green and blue light emission. The same technique can also be used for OLEDs. The white OLED may be a single light emitting layer (EML) device or a stack structure. Color can be measured using CIE coordinates well known in the art.

summary

In one aspect, the present disclosure provides a compound comprising a _{ligand L A of Formula I:}

here:

A ¹ and A ² is each independently a monocyclic or polycyclic fused ring system comprising at least one fused or unfused 5- or 6-membered carbocyclic or heterocyclic ring;

And X ¹ -X ⁴ are each independently C or N, stage, at least one of X ¹ -X ⁴ is C, X ¹ -X ^4, at least one of which is N;

K ¹ and each K ² is independently selected from the group consisting of a direct bond, O, and S;

L ¹ is selected from the group consisting of a single bond, O, S, C=R', CR'R", SiR'R", GeRR', BR', BR'R", and NR';

R ^A and each R ^D represents unsubstituted, monosubstituted, or up to the maximum permissible substitution for its related ring;

R ^A and At least one of R ^{D is the corresponding A 1} and has the structure of formula II fused to A ^{2 :}

;

;

Z ¹ -Z ⁴ are each independently selected from the group consisting of CRR', SiRR', and GeRR', with the proviso ^{that at least one of Z 1} -Z ⁴ is GeRR' or SiRR';

n = 0 or 1;

n is 1 and A ¹ or when A ² is a pyridine ring fused to Formula II, ^{at least two of Z 1} -Z ⁴ are GeRR′ or SiRR′;

each R ^A , R ^D , R , and R′ is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof a substituent selected from the group consisting of;

Ligand L _A forms a complex with metal M via the dashed line to form a 5-membered chelate ring;

M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;

M may be coordinated to another ligand;

L _A can be linked to another ligand to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;

Any two adjacent R ^A , R ^D , R , and R′ may be joined or fused to form a ring.

In another aspect, the present disclosure provides combinations of compounds comprising a _{ligand L A of Formula (I) disclosed herein.}

In another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a _{ligand L A of Formula I disclosed herein.}

In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound comprising a _{ligand L A of Formula I disclosed herein.}

1 shows an organic light emitting device.
2 shows an inverted organic light emitting device without a separate electron transport layer.
3 depicts the normalized PL spectra of the inventive and comparative compounds for PMMA.

A. Terms

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

As used herein, the term “organic” includes small molecule organic materials as well as polymeric materials that can be used to fabricate organic optoelectronic devices. “Small molecule” refers to any organic material that is not a polymer, and a “small molecule” may actually be quite large. Small molecules may, in some circumstances, contain repeating units. For example, the use of a long chain alkyl group as a substituent does not exclude the molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example, as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core moiety of a dendrimer consisting of a series of chemical shells created on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule", and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When a first layer is described as being “disposed over” a second layer, the first layer is disposed remote from the substrate. Other layers may exist between the first layer and the second layer unless the first layer is specified as being “in contact” with the second layer. For example, the cathode may be described as “disposed over” the anode, although there are various organic layers 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 solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of the luminescent material. Although the auxiliary ligand may alter the properties of the photoactive ligand, a ligand may be referred to as “auxiliary” if the ligand is not believed to contribute to the photoactive properties of the luminescent material.

As used herein, and as generally understood by one of ordinary skill in the art, a first “highest occupied molecular orbital” (HOMO) or “least unoccupied molecular orbital” (HOMO) when the first energy level is closer to the vacuum energy level. The (LUMO) energy level is “greater than” or “higher” than the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with a vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of the diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as will generally be understood by one of ordinary skill in the art, the first workfunction is “greater than” or “higher” than the second workfunction if the absolute value of the first workfunction is greater. Since workfunctions are usually measured as negative numbers with respect to the vacuum level, this means that "higher" workfunctions are more negative. In a typical energy level diagram with a vacuum level at the top, a "higher" workfunction is illustrated as further down from the vacuum level. Thus, the definition of HOMO and LUMO energy levels follows a different convention than work functions.

The terms “halo”, “halogen” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)—R _s ).

The term “ester” refers to a substituted oxycarbonyl (—OC(O)—R _s or —C(O)—OR _s ) radical.

The term “ether” refers to the _{—OR s radical.}

The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to the _{-SR s radical.}

The term “sulfinyl” refers to the —S(O)—R _s radical.

The term “sulfonyl” refers to the _{—SO 2} —R _{s radical.}

The term “phosphino” refers to the —P(R _s ) ₃ radical, wherein each R _s may be the same or different.

The term “silyl” refers to the —Si(R _s ) ₃ radical, wherein each R _s may be the same or different.

The term “boryl” refers to a —B(R _s ) ₂ radical or a Lewis adduct thereof —B(R _s ) ₃ radical, where R _s may be the same or different.

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

The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. 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. etc. Additionally, a cycloalkyl group may be optionally substituted.

The term “heteroalkyl” or “heterocycloalkyl” refers to an alkyl or cycloalkyl radical having one or more carbon atoms each substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, a heteroalkyl or heterocycloalkyl group may be optionally substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. An alkenyl group is essentially an alkyl group containing one or more carbon-carbon double bonds in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising one or more carbon-carbon double bonds within the cycloalkyl ring. As used herein, the term “heteroalkenyl” refers to an alkenyl radical having one or more carbon atoms substituted by a heteroatom. Optionally, one or more heteroatoms are 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 2 to 15 carbon atoms. Additionally, an alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. An alkynyl group is essentially an alkyl group containing one or more carbon-carbon triple bonds in the alkyl chain. Preferred alkynyl groups are those containing from 2 to 15 carbon atoms. Additionally, an alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, an aralkyl group may be optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing one or more heteroatoms. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteraromatic cyclic radicals may also be used interchangeably with heteroaryl. Preferred heterononaromatic cyclic groups contain one or more heteroatoms and include cyclic amines such as morpholino, piperidino, pyrrolidino and the like, and cyclic ethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. / those containing 3 to 7 ring atoms, including thio-ethers. Additionally, heterocyclic groups may be optionally substituted.

The term “aryl” refers to and includes both single ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. A polycyclic ring may have two or more rings in which two carbons are common to two adjacent rings (these rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbyl group, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. Preferred aryl groups are those containing from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, more preferably from 6 to 12 carbon atoms. Particular preference is given to aryl groups having 6, 10 or 12 carbons. Suitable aryl groups are phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl , triphenyl, triphenylene, fluorene and naphthalene. Additionally, the aryl group may be optionally substituted.

The term "heteroaryl" includes both single ring aromatic groups and polycyclic aromatic ring systems containing one or more heteroatoms. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N is a preferred heteroatom. The hetero single ring system is preferably a single ring having 5 or 6 ring atoms, and the ring may have 1 to 6 heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two carbons are common to two adjacent rings (these rings are "fused"), wherein at least one of the rings is heteroaryl, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. The hetero polycyclic aromatic ring system may have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 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, oxathia Gin, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine , pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, Preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine , 1,4-azaborine, borazine and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, Of particular interest are the groups of triazines, and benzimidazoles, and their respective individual aza-analogs.

As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic groups, aryl and heteroaryl are independently unsubstituted; or independently substituted with one or more common substituents.

In many cases, common substituents are deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

In some cases, preferred general substituents are deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, 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, boyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

In other instances, 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 a substituent other than H that is attached to the relevant position, such as carbon or nitrogen. For example, when R ¹ represents mono-substitution, one R ¹ must be other than H (ie, substitution). Similarly, when R ¹ represents disubstitution, ^{two of R 1} must be other than H. Similarly, when R ¹ represents zero substitution or unsubstituted, R ¹ may be hydrogen with respect to the available valencies of the ring atoms, for example the carbon atom of benzene and the nitrogen atom of pyrrole, or simply fully charged. Nothing may be shown for a ring atom having a valence, such as the nitrogen atom of pyridine. The maximum number of substitutions possible in a ring structure depends on the total number of valences available at the ring atoms.

As used herein, "combination thereof" indicates that one or more elements of the corresponding list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art would envision from that list. For example, alkyl and deuterium may be combined to form a partially or fully deuterated alkyl group; Halogen and alkyl may be combined to form a halogenated alkyl substituent; Halogen, alkyl, and aryl may be combined to form a halogenated arylalkyl. In one instance, the term substitution includes combinations of 2 to 4 of the listed groups. In other instances, the term substitution includes combinations of two to three groups. In another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those containing up to 40 atoms that are not hydrogen or deuterium, or those containing up to 30 atoms that are not hydrogen or deuterium. . In many cases, a preferred combination of substituents will include up to 20 atoms that are not hydrogen or deuterium.

The designation "aza" in the fragments described herein, i.e. azadibenzofuran, azadibenzothiophene, etc., means that one or more of the CH groups in each aromatic ring may be replaced with a nitrogen atom, for example Azatriphenylene includes, but is not limited to, both dibenzo[ f,h ]quinoxaline and dibenzo[ f,h]quinoline. One of ordinary skill in the art can readily contemplate other nitrogen analogs of the aza-derivatives described above, all of which are intended to be encompassed by the terms 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, incorporated herein by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. are doing Further literature [Ming Yan, et al ., Tetrahedron 2015, 71, 1425-30] and Atzrodt et al ., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated herein by reference in their entirety, which describe efficient routes for the deuteration of methylene hydrogens in benzyl amines and replacement of aromatic ring hydrogens with deuterium, respectively. are doing

When a molecular segment is described as being a substituent or otherwise attached to another moiety, its designation is as if it were a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., for example, benzene, naphthalene, dibenzofuran). As used herein, different designations of such substituents or attached segments are considered equivalent.

In some cases, pairs of adjacent substituents may optionally be joined (linked) or fused to form a ring. Preferred rings are 5-, 6- or 7-membered carbocyclic or heterocyclic rings, including both cases in which a part of a ring formed by a pair of substituents is saturated and a case in which a part of a ring formed by a pair of substituents is unsaturated. . As used herein, "adjacent" means having the two closest substitutable positions, such as the 2, 2' position of biphenyl, or the 1, 8 position of naphthalene, so long as they are capable of forming a stable fused ring system. This means that two substituents may be present next to each other on two neighboring rings, or on the same ring.

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a compound comprising a _{ligand L A of Formula I:}

here:

A ¹ and A ² is each independently a monocyclic or polycyclic fused ring system comprising at least one fused or unfused 5- or 6-membered carbocyclic or heterocyclic ring;

And X ¹ -X ⁴ are each independently C or N, stage, at least one of X ¹ -X ⁴ is C, X ¹ -X ^4, at least one of which is N;

K ¹ and each K ² is independently selected from the group consisting of a direct bond, O, and S;

L ¹ is selected from the group consisting of a single bond, O, S, C=R', CR'R", SiR'R", GeRR', BR', BR'R", and NR';

R ^A and each R ^D represents unsubstituted, monosubstituted, or up to the maximum permissible substitution for its related ring;

R ^A and At least one of R ^{D is the corresponding A 1} and has the structure of formula II fused to A ^{2 :}

;

;

Z ¹ -Z ⁴ are each independently selected from the group consisting of CRR', SiRR', and GeRR', with the proviso ^{that at least one of Z 1} -Z ⁴ is GeRR' or SiRR';

n = 0 or 1;

n is 1 and A ¹ or when A ² is a pyridine ring fused to Formula II, ^{at least two of Z 1} -Z ⁴ are GeRR′ or SiRR′;

each R ^A , R ^D , R , and R′ is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof a substituent selected from the group consisting of;

Ligand L _A forms a complex with metal M via the dashed line to form a 5-membered chelate ring;

M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;

M may be coordinated to another ligand;

L _A can be linked to another ligand to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;

Any two adjacent R ^A , R ^D , R , and R′ may be joined or fused to form a ring.

In some embodiments, a compound of the present disclosure comprises a ligand L ^A of Formula IV:

wherein ring A ¹ , ring A ² , X ¹ -X ⁴ , R ^A and R ^D is defined above.

In some embodiments, each R ^A , R ^D , R , and R′ is independently hydrogen, or a generic or preferred generic substituent disclosed above.

In some embodiments, n is 0. In some embodiments, n is 1.

In some embodiments, K ¹ is a direct bond. In some embodiments, K ² is a direct bond. In some embodiments, K ¹ is O. In some embodiments, K ² is O. In some embodiments, K ¹ is S. In some embodiments, K ² is S. In some embodiments, L ¹ is a direct bond. In some embodiments, L ¹ is O. In some embodiments, L ¹ is S. In some embodiments, L ¹ is CR′R″. In some embodiments, L ¹ is SiR′R″. In some embodiments, L ¹ is BR′. In some embodiments, L ¹ is NR′. In some embodiments, K ¹ and one of K ² is a direct bond, and K ¹ and The other of K ² is O or S. In some embodiments, L ¹ , K ¹ , K ² are all direct bonds. In some embodiments, L ¹ is a direct bond, and K ¹ and one of K ² is a direct bond, and K ¹ and The other of K ² is O or S. In some embodiments, L ¹ is a direct bond, and K ¹ and one of K ² is a direct bond, and K ¹ and The other of K ² is O or S. In some embodiments, L ¹ is O, S, C = R ' , CR'R ", SiR'R", GeRR', BR is selected from the group consisting of ', BR'R ", and NR'; K ¹ and Both K ² are direct bonds.

In some embodiments, A ¹ and one of A ² is benzene, A ¹ and The other of A ² is selected from the group consisting of pyrimidine, pyridine, pyridazine, triazine, pyrazine, benzene, imidazole, pyrazole, oxazole, thiazole, and N-heterocyclic carbene.

In some embodiments ^{, one of Z 1} -Z ⁴ is SiRR′ and the other of Z ¹ -Z ⁴ is CRR′.

In some embodiments, two of Z ¹ -Z ⁴ are SiRR′ and the other of Z ¹ -Z ⁴ are CRR′.

In some embodiments, R and R′ are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In some embodiments, when R and R' are attached to the same Si atom, R and R' are joined together to form a ring.

In some embodiments, X ¹ is N and X ² , X ³ , and X ⁴ are each C.

In some embodiments, one or more R ^D substituents are alkyl.

In some embodiments, M is Ir.

In some embodiments, the compound further comprises a substituted or unsubstituted acetylacetonate ligand.

In some embodiments, ligand L _A is selected from the group consisting of the structures of List A:

here:

T is selected from the group consisting of B, Al, Ga, and In;

each of Y ¹ to Y ¹³ is independently selected from the group consisting of carbon and nitrogen;

Y' is selected from the group consisting _{of BR e} , NR _e , PR _e , O, S, Se, C=O, S=O, SO ₂ , CR _e R _f , SiR _e R _f , and GeR _e R _{f ;} ;

R _e and R _f may be fused or joined to form a ring;

each R _a , R _b , R _c , and R _d independently represents unsubstituted, monosubstituted, or up to the maximum permissible number of substitutions for its associated ring;

R _a1 , R _b1 , R _c1 , R _d1 , R _a , R _b , R _c , R _d , R _e and each of R _f is independently hydrogen, or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl , aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; a substituent selected from the group consisting of general substituents as defined herein;

any two adjacent R _a , R _b , R _c , R _d , R _e and R _f may be fused or joined to form a ring or a polydentate ligand.

In some embodiments, ligand L _A is selected from the group consisting of the structures of List B:

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

wherein R, R' may form a ring; R and R' are selected from the group consisting of:

In some embodiments, ligand L _A is selected from the group consisting of the structure of List C:

where i is an integer from 1 to 688, wherein for each i , R ^E and G is defined in Table 1 below:

wherein R ¹ to R ⁴³ have the following structure:

wherein G ¹ to G ²² have the following structure:

In some embodiments, the compound has the formula M (L _{A) x} (L _{B) y (C} L) _z, wherein L and _B each L _C is a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x+y+z is the oxidation state of metal M.

In some embodiments, the compound is _{Ir (L A) 3, Ir} (L A) (L B) 2, Ir (L A) 2 (L B), Ir (L A) 2 (L C), and Ir ( L _a) (having a formula selected from the group consisting of L _B) (L _C); wherein L _A , L _B , and L _C are different from each other.

In some embodiments, the compound has the general formula _{Pt (L A) (L B} ); L _A and L _B may be the same or different.

In some embodiments, L _A and L _B forms a 4 L ligand is associated.

In some embodiments, L _A and L _B is connected in two places to form a click 4 L ligand during marking.

In some embodiments, L _B is selected from the group consisting of a structure of the list A defined above.

In some embodiments, _B and L each L _C is independently selected from the group consisting of the structures of List D:

wherein R _a ', R _b ', R _c ', R _d ', R _e ', R _f ', R _g ', and R _n ' are each independently unsubstituted, mono-substituted, or up to the maximum permissible substitution;

R _a ', R _b ', R _c ', R _d ', R _e ', R _f ', R _g ', and R _n ' are each independently hydrogen, or deuterium, halide, alkyl, cycloalkyl, hetero Alkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sul a substituent selected from the group consisting of panyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

Two adjacent R _a ', R _b ', R _c ', R _d ', R _e ', R _f ', R _g ', and R _n ' are fused or joined to form a ring or a polydentate ligand. can;

R _a , R _b , and R _c are all defined as above, each of which may form a ring with the other, if chemically possible.

Formula _{M (L A) x (L} B) y (L C) and in a part of the compound embodiments having a _z mode, L _B is selected from the group consisting of L _{B k,} where k is an integer from 1 to 270, L _B1 to L _B270 have the structures defined in List E below:

Formula _{M (L A) x (L} B) y (L C) In some embodiments of compounds with _z, L _B is _{L B1, L B2, L B18} , L B28, L B38, L B108, L B118, _{L B122, L B124, L B126} , L B128, L B130, L B132, L B134, L B136, L B138, L B140, L B142, L B144, L B156, L B158, L B160, L B162, L B164 _{, L B168, L B172, L} B175, L B204, L B206, L B214, L B216, L B218, L B220, L B222, L B231, L B233, L B235, L B237, L B240, L B242, L _{B244, L B246, L B248,} L B250, L B252, L B254, L B256, L B258, L B260, L B262, L B263, L B264, L B265, L B266, L B267, L B268, L B269, and L _B270 .

Formula _{M (L A) x (L} B) y (L C) In some embodiments of compounds with _z, L _B is _{L B1, L B2, L B18} , L B28, L B38, L B108, L B118, _{L B122, L B126, L B128} , L B132, L B136, L B138, L B142, L B156, L B162, L B204, L B206, L B214, L B216, L B218, L B220, L B231, L B233 , L _{B 237, B 264} L, is selected from the group consisting of L _{B265, B266} L, L _{B267, B268} L, L _{B269, B270} and L.

에 기초한 L_C1-I 내지 L_C1416-I의 화합물로 구성되고, L_{C j -II}는

의 구조에 기초한 L_C1-II 내지 L_C1416-II의 화합물로 구성되며, 여기서 L_{C j -I} 및 L_{C j -II}에서 각각의 L_{C j} 에 대해, R²⁰¹ 및 R²⁰²는 각각 독립적으로 하기 표 2에 정의되어 있다:Formula _{M (L A) x (L} B) y In some embodiments of the compounds having the (L _{C) z, C} L is an unsubstituted or substituted acetylacetonato ligand. In some embodiments, L _C is L _{C j -I} and L _{C j -II} is selected from the group consisting of, wherein j is an integer from 1 to 1416, wherein L _{C j -I} is

Consists of a compound of _{L C1-I} to L _C1416-I based on L _{C j -II} is

It consists of compounds of _{L C1-II} to L _C1416-II based on the structure of _{L C j -I} and In the L _{j -II C} for each _{C j} L, R ²⁰¹ and R ²⁰² is each independently defined in Table 2:

where R ^D1 to R ^D246 have the structure of List F below:

Formula _{M (L A) x (L} B) y (L C) In some embodiments of compounds with _z, ligand L _C L _C is only these _{j -I} or L _{C j -II} ligands and their corresponding R ²⁰¹ and R ²⁰² is defined as being one of the following structures: R ^D1 , R ^D3 , R ^D4 , R ^D5 , R ^D9 , R ^D10 , R ^D17 , R ^D18 , R ^D20 , R ^D22 , R ^D37 , R ^D40 , R ^D41 , R ^D42 , R ^D43 , R ^D48 , R ^D49 , R ^D50 , R ^D54 , R ^D55 , R ^D58 , R ^D59 , R ^D78 , R ^D79 , R ^D81 , R ^D87 , R ^D88 , R ^D89 , R ^D93 , ^{R D116, R D117, R D118} , R D119, R D120, R D133, R D134, R D135, R D136, R D143, R D144, R D145, R D146, R D147, R D149, R D151, R D154 , R ^D155 , R ^D161 , R ^D175 R ^D190 , R ^D193 , R ^D200 , R ^D201 , R ^D206 , R ^D210 , R ^D214 , R ^D215 , R ^D216 , R ^D218 , R ^D219 , R ^D220 , R ^D227 , R ^D237 , R ^D241 , R ^D242 , R ^D245 , and R ^D246 .

Formula _{M (L A) x (L} B) y (L C) In some embodiments of compounds with _z, ligand L _C L _C is only these _{j -I} or L _{C j -II} ligands and their corresponding R ²⁰¹ and R ²⁰² is defined as one selected from the following structures: R ^D1 , R ^D3 , R ^D4 , R ^D5 , R ^D9 , R ^D10 , R ^D17 , R ^D22 , R ^D43 , R ^D50 , R ^D78 , R ^D116 , ^{R D118, R D133, R D134} , R D135, R D136, R D143, R D144, R D145, R D146, R D149, R D151, R D154, R D155 R D190, R D193, R D200, R D201, R ^D206 , R ^D210 , R ^D214 , R ^D215 , R ^D216 , R ^D218 , R ^D219 , R ^D220 , R ^D227 , R ^D237 , R ^D241 , R ^D242 , R ^D245 , and R ^D246 .

To the formula _{M (L A) x (L} B) y In some embodiments of the compounds having the (L _{C) z, C} ligand L can be selected from the group consisting of the formula:

In some embodiments, the compound of the general formula _{Ir (L A i - m)} 3 Ir based on (L _{A 1 - 1) 3} to Ir (L _{A688-68) 3;} Based on the general formula Ir(L _{A i - m} )(L _{B k} ) _{2 Ir (L A 1 - 1)} (L B 1) 2 to _{Ir (L A688-68) (L B} 270) 2; Formula _{Ir - (- 1 L A 1} ) 2 (L C 1-I) to _{Ir (L A668-68) 2 (L} C 1416-I) (L A i m) 2 (L C jI) Ir based on ; And the formula _{Ir (L A i - m)} 2 Ir based on _{(L C j-II) (} L A 1 - 1) 2 (L C 1-II) to _{Ir (L A688-68) 2 (L} C 1416 _-II ) is selected from the group consisting of; where i is an integer from 1 to 688, m is an integer from 1 to 68, k is an integer from 1 to 270, j is an integer from 1 to 1416, L _{A i - m} , L _{B k} , L _{C jI} , and L _{C j-II} are as defined above.

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

In some embodiments, the compound of the general formula _{Ir L B (- (68 L} A 668) (L A i - - m) (L B) formula based on _{2 Ir (L A 1 1)} (L B) 2 to Ir ) may have a _2, where L _{a i - m} is L _{a 1} previously described _{- 1} to L _{a 688 -} is a structure selected from the group consisting of _68, L _B is selected from the group consisting of a structure of the list a .

In some embodiments, compounds have the general formula _{Ir (L A) (L B} k) formula based on _{2 Ir (L A) (L} B 1) 2 to _{Ir (L A) (L B} 2770) 2 , and where L _a have the above-mentioned general formula I, L _{B k} shows the structure of L _B1 to L _B270 as described above.

In some embodiments, the compound of the general formula _{Ir (L A i - m)} 2 (L B) Formula Ir based on _{(L A 1 - 1) 2} (L B) to _{Ir (L A 688 - 68)} 2 (L _B) a may have, where L _{a i - m} is L _{a 1} as described above _{- 1} to L _{a 688-represents} the group consisting of _68, L _B is selected from the group consisting of structures listed in the list a .

In some embodiments, compounds have the general formula _{Ir (L A) 2 (L} B k) the formula _{Ir (L A) 2 (L} B 1) to _{Ir (L A) 2 (L} B 270) based on, and where L _a have the above-mentioned general formula I, L _{B k} represents one of the structure of L ₁ to L _{B B 270} as described above.

In some embodiments, the compound of the general formula _{Ir - (- 1 L A 1} ) 2 (L C) to _{Ir (L A i m) 2} (L C) formula Ir based on _{(L A 688 - 68) 2} (L _C ), wherein L _{A i - m} represents the group consisting of L _{A 1 - 1} to L _{A 688 - 68 as described above, and L C} is selected from the group consisting of the structures listed in List B above. .

In some embodiments, the compound of the general formula _{Ir (L A) 2 (L} C j -I) formula Ir (L _A) based on the ₂ (L _{C 1 -I)} to _{Ir (L A) 2 (L} C 1416 - _I ), wherein L _A has the above-mentioned formula I, and L _{C j -I is L C 1 -I} to L C 1 -I as described above It represents one of the structures of _{L C 1416 -I.}

In some embodiments, the compound of the general formula _{Ir (L A) 2 (L} C j -II) formula _{Ir (L A) 2 (L} C 1 -II) to _{Ir (L A) 2 (L} C 1416 based on the _{- II} ), wherein L _A has the aforementioned formula I, and L _{C j -II} represents one of the structures of _{L C 1 -II} to L _{C 1416 -II} as described above.

In some embodiments, the compound has Formula III:

here:

M ¹ is Pd or Pt;

moieties E and F are each independently a monocyclic or polycyclic ring structure comprising 5- and/or 6-membered carbocyclic or heterocyclic rings;

Z ¹ and each Z ² is independently C or N;

K ¹ , K ² , K ³ , and K ⁴ are each independently selected from the group consisting of a direct bond, O, and S, at least two of which are direct bonds;

L ¹ , L ² , L ³ and each L ⁴ is independently selected from the group consisting of a single bond, no bond, O, S, CR'R", SiR'R", BR', and NR', L ¹ , L ² , L ³ and at least 3 of L ^{4 are present;}

R ^E and each R ^F independently represents unsubstituted, monosubstituted, or up to the maximum permissible number of substitutions for its related ring;

each of R′, R″, R ^E , and R ^F is independently hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl , a substituent selected from the group consisting of heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;

two adjacent R ^A , R ^D , R ^E , and R ^F , where chemically possible, may be joined together or fused together to form a ring;

X ¹ -X ⁴ , R ^A , R ^D and ring A ¹ and A ² is all defined in the same manner as above. In some embodiments, Ring E and Ring F are both 6 membered aromatic rings.

In some embodiments, Ring F is a 5 or 6 membered heteroaromatic ring. In some embodiments, L ² is O or CR'R". In some embodiments, Z ² is N and Z ¹ is C. In some embodiments, Z ² is C and Z ¹ is N. In some embodiments, L ³ is a direct bond. In some embodiments, L ³ is NR'. In some embodiments, K ¹ , K ² , K ³ , and K ⁴ are all a direct bond. Some embodiments In , one of K ¹ , K ² , K ³ , and K ⁴ is O.

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

here:

R ^x and each R ^y is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

R ^G at each occurrence is independently hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl , a substituent selected from the group consisting of nitrile, isonitrile, sulfanyl, and combinations thereof;

X ¹ -X ⁴ , R ^A , R ^D and rings A ¹ and A ² are all defined as above.

C. OLEDs and devices of the present disclosure

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

In some embodiments, the first organic layer may comprise a compound comprising a _{ligand L A of Formula (I).}

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

In some embodiments, the organic layer may further comprise a host, wherein the host comprises triphenylene containing benzo fused thiophene or benzo fused furan, and any substituents in the host are independently 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 , and C _n H _2n -Ar ₁ is a non-fused substituent selected from the group consisting of, or the host has no substituents, where n is 1 to 10; Ar ₁ and Ar ₂ are 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, the host being triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa- 13b-boranaphtho [3,2,1-de] anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-di benzoselenophene, and at least one chemical group selected from the group consisting of aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

In some embodiments, the host may be selected from the group of hosts consisting of the following structures and combinations thereof:

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

In some embodiments, the compounds described herein may be sensitizers; The device may further include an acceptor, and the acceptor may be selected from the group consisting of a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

In another aspect, an OLED of the present disclosure may also include a light emitting region containing a compound disclosed in the Compounds section above of the present disclosure.

In some embodiments, the light emitting area may comprise a compound comprising a ligand L _A of formula I.

In some embodiments, at least one of the anode, cathode, or new layer disposed over the organic light emitting layer functions as a reinforcement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively binds to the emitter material and transfers the excited state energy from the emitter material to the surface plasmon polariton in a non-radiative mode. The enhancement layer is provided within a critical distance from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radioactive decay rate constant due to the presence of the enhancement layer, and the critical distance is such that the total non-radiative decay rate constant is equal to the total radioactive decay rate. Same place as constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the reinforcement layer on the opposite side of the organic light emitting layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emissive layer from the enhancement layer but still outcouples 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 in free space as photons. In other embodiments, energy is scattered from surface plasmon modes to other modes of the device, such as, but not limited to, organic waveguide modes, substrate modes, or other waveguide modes. If energy is scattered into the non-free space mode of the OLED, other outcoupling schemes can be incorporated to extract that energy into free space. In some embodiments, one or more intervening layers may be disposed between the reinforcement layer and the outcoupling layer. Examples of intervening layer(s) 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 is present, resulting in any or all of the following: a decrease in the rate of emission, a change in the shape of the emission line, a change in the emission intensity with angle, a change in the stability of the emitter material. , changes in the efficiency of OLEDs, and reduced efficiency roll-offs of OLED devices. Placing an enhancement layer on the cathode side, the anode side, or both creates an OLED device that exploits any of the aforementioned effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, OLEDs according to the present disclosure may include any other functional layers commonly found in OLEDs.

The reinforcement layer may be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. 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 this embodiment the metal is Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys of these materials. or mixtures, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, in which the entire medium behaves differently than the sum of its material parts. In particular, the applicant defines an optically active metamaterial as a material having both a negative dielectric constant and a negative transmittance. On the other hand, the hyperbolic metamaterial is an anisotropic medium having a different sign with respect to a spatial direction with different permittivity or transmittance. Optically active metamaterials and hyperbolic metamaterials are strictly distinct from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium must appear uniformly in the direction of propagation on the wavelength-length scale of light. do. Using terms understood by one of ordinary skill in the art: the dielectric constant of a metamaterial in the direction of propagation can be described as an effective medium approximation. Plasmonic materials and metamaterials provide a way to control the propagation of light that can improve OLED performance in a variety of ways.

In some embodiments, the reinforcement layer is provided as a planar layer. In other embodiments, the reinforcement layer has features of wavelength size that are arranged periodically, quasi-periodically, or randomly, or features of subwavelength size that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features, or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features. In some embodiments, the outcoupling layer may be comprised of a plurality of nanoparticles and in other embodiments the outcoupling layer is comprised of a plurality of nanoparticles disposed over the material. Outcoupling in these embodiments comprises 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; adjustable by at least one of changing the refractive index of the material or additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcement layer, and/or changing the material of the reinforcement layer. The plurality of nanoparticles of the device are coated with a shell of a different type of material as a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack or layer of one or more materials, and/or a core of one material. It may be formed of at least one of the cores. In some embodiments, the outcoupling layer comprises: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, at least one nanoparticle selected from the group consisting of Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layers disposed thereon. In some embodiments, the polarization of light emission can be tuned using an outcoupling layer. By varying the dimension and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments the outcoupling layer also acts as an electrode of the device.

In another aspect, the present disclosure also provides an anode; cathode; and an organic light emitting device (OLED) having an organic layer disposed between an anode and a cathode, wherein the organic layer can include a compound disclosed in the Compounds section above of the present disclosure.

In some embodiments, the consumer product comprises an anode; cathode; And an organic light emitting device (OLED) having an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound comprising a ligand L _A of formula (I) described herein.

In some embodiments, the consumer product is a flat panel display, computer monitor, medical monitor, television, billboard, indoor or outdoor lighting and/or signaling light, head-up display, fully or partially transparent display, flexible display, laser printer, telephone, Cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro displays less than 2 inches diagonal, 3D displays, virtual or augmented reality displays, vehicles, tiling together It may be one of a video wall comprising multiple tiled displays, a theater or stadium screen, a phototherapy device, and a signage.

Generally, OLEDs include one or more organic layers disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes into the organic layer(s) and the cathode injects electrons. The injected holes and electrons move toward oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, “excitons,” which are localized electron-hole pairs with excited energy states, are created. Light is emitted when the exciton is relaxed via a light emission mechanism. In some cases, excitons may localize on excimers or exciplexes. Non-radiative mechanisms such as thermal relaxation may also occur, but are generally considered undesirable.

Various OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

Early OLEDs used light-emitting molecules that emit light (“fluorescence”) from a singlet state, as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs with emissive materials that emit light from the triplet state (“phosphorescence”) have been presented. See Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I")] and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II")] is incorporated by reference in its entirety. Phosphorescence is described more specifically at columns 5-6 of US Pat. No. 7,279,704, which is incorporated by reference.

1 shows an organic light emitting device 100 . The drawings are not necessarily drawn to scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, an electron transport layer ( 145 ), an electron injection layer 150 , a passivation layer 155 , a cathode 160 , and a barrier layer 170 . The cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164 . Device 100 may be fabricated by depositing the layers in the order described. These various layers, as well as the properties and functions of exemplary materials, are more specifically described in columns 6-10 of US Pat. No. 7,279,704, which is incorporated by reference.

More examples for each of these layers are also available. For example, a flexible and transparent substrate-anode combination is disclosed in US Pat. No. 5,844,363, which is incorporated by reference in its entirety. As an example of a p-doped hole transport layer, as disclosed in US Patent Application Publication No. 2003/0230980, m-MTDATA is _{doped with F 4} -TCNQ in a molar ratio of 50:1, and this patent document discloses that The full text is incorporated by reference. Examples of luminescent and host materials are disclosed in US Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, provide examples of cathodes, including compound cathodes having thin layers of metals such as Mg:Ag with laminated transparent, electrically conductive sputter-deposited ITO layers. has been disclosed. The theory and use of barrier layers are more specifically described 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. An example of an injection layer is provided in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

2 shows an inverted structure OLED 200 . The device includes a substrate 210 , a cathode 215 , a light emitting layer 220 , a hole transport layer 225 and an anode 230 . Device 200 may be fabricated by depositing the layers in the order described. Since the most common OLED configuration is one with the cathode disposed above the anode, and the device 200 has the cathode 215 disposed below the anode 230, the device 200 will be referred to as an “inverted” OLED. can Materials similar to those described with respect to device 100 may be used for that layer of device 200 . 2 provides an example of how some layers may be omitted from the structure of device 100 .

The simple stacked structures shown in FIGS. 1 and 2 are provided by way of non-limiting example, and it is understood that embodiments of the present disclosure may be used in connection with a variety of other structures. The specific materials and structures described are illustrative in nature, and other materials and structures may be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or layers can 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 various layers as comprising a single material, it is understood that combinations of materials, such as mixtures of host and dopant, or more generally mixtures, may be used. In addition, 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 a plurality of layers of different organic materials, for example as described in connection with FIGS. 1 and 2 .

Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) comprising polymeric materials as disclosed in U.S. Patent No. 5,247,190 (Friend et al.), which is incorporated by reference in its entirety. . As a further example, it is possible to use an OLED having a single organic layer. OLEDs may be stacked, for example, as described in US Pat. No. 5,707,745 (Forrest et al.), which is incorporated herein by reference in its entirety. The OLED structure may deviate from the simple stacked structure shown in FIGS. 1 and 2 . For example, the substrate may have a mesa structure as described in US Pat. No. 6,091,195 (Forrest et al.) and/or an outcoupling such as a pit structure as described in US Pat. No. 5,834,893 (Bulovic et al.). may include an angled reflective surface to improve

Unless otherwise indicated, any layer of the various embodiments may be deposited by any suitable method. For the organic layer, preferred methods include thermal evaporation as described in US Pat. Nos. 6,013,982 and 6,087,196 (which are incorporated by reference in their entirety), ink-jet, US Pat. Organic vapor deposition (OVPD) as described in (this patent document is incorporated by reference in its entirety) and organic vapor jet printing as described in US Pat. No. 7,431,968, which is incorporated by reference in its entirety. vapor deposition by (OVJP) is mentioned. Other suitable deposition methods include spin coating and other solution based processes. The solution-based process is preferably carried out in nitrogen or in an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred methods of pattern formation include deposition through a mask, cold welding as described in US Pat. pattern formation associated with some deposition methods, such as Other methods may also be used. A material to be deposited may be modified to be compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, preferably containing 3 or more carbons, can be used in small molecules to enhance their solution processing capability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being the preferred range. Because an asymmetric material may have a lower recrystallization tendency, a material having an asymmetric structure may have better solution processability than a material having a symmetric structure. Dendrimer substituents can be used to improve the solution processing capability of small molecules.

Devices fabricated according to embodiments of the present disclosure may optionally further include a barrier layer. One purpose of barrier layers is to protect electrodes and organic layers from damage due to exposure to harmful species in environments containing moisture, vapors and/or gases, and the like. The barrier layer may be deposited over any other portion of the device, including the edge, over, under, or next to the electrode or substrate. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by a variety of known chemical vapor deposition techniques and may include a composition having a single phase as well as a composition having a plurality of phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may include inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials as described in US Pat. No. 7,968,146, PCT Patent Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are incorporated by reference in their entirety. incorporated herein by To be considered a "mixture", the aforementioned polymeric and non-polymeric materials comprising the barrier layer must be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymer to non-polymeric material may be in the range of 95:5 to 5:95. Polymeric and non-polymeric materials can 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 fabricated in accordance with embodiments of the present disclosure may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated within various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light emitting devices, such as individual light source devices or lighting panels, etc. that can be used by end consumer product producers. Such electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure may be incorporated into a wide variety of consumer products that include one or more electronic component modules (or units) therein. A consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer within the OLED is disclosed. Such consumer products would include any kind of product including one or more light source(s) and/or one or more visual displays of any kind. Some examples of such consumer products are flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, head-up displays, fully or partially transparent displays, flexible displays, rollable displays. , foldable displays, stretchable displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro displays (2 inches diagonally) displays), 3D displays, virtual or augmented reality displays, vehicles, video walls including multiple displays tiled together, theater or stadium screens, phototherapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated in accordance with the present disclosure. Many devices are intended for use in a temperature range conducive to human comfort, such as 18°C to 30°C, more preferably room temperature (20°C to 25°C), but outside this temperature range, such as -40°C to +80°C. can also be used in

Further details and the foregoing definitions of OLEDs can be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices, such as organic transistors, may use the above materials and structures.

In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and curved properties. 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 comprises an arrangement of RGB pixels, or an arrangement of white plus color filter pixels. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel that is less than 10 inches diagonal or less than 50 square inches in area. In some embodiments, the OLED is a display panel with a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is a lighting panel.

In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound is phosphorescent, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as type E delayed fluorescence; eg, U.S. Patent Application Serial No. 15/ 700,352), triplet-triplet extinction, or a combination of these processes can produce luminescence. In some embodiments, the luminescent dopant may be a racemic mixture, or may be enriched in one enantiomer. In some embodiments, the compound may be homoligand (each ligand is the same). In some embodiments, the compound may be heterologous (at least one ligand differs from the other). Where there is more than one ligand coordinated to the metal, the ligands may all be identical in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, all ligands may be different from each other. This is also true for embodiments in which a ligand coordinated to a metal can be linked with another ligand coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, when coordinating ligands are linked together, all ligands may be the same in some embodiments, and at least one of the linked ligands may be different from the other ligand(s) in some other embodiments.

In some embodiments, the compound may be used as a phosphorescent sensitizer in an OLED, wherein one or a plurality of layers in the OLED contain one or more acceptors in the form of fluorescent and/or delayed fluorescent emitters. In some embodiments, the compound may be used as one component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to an acceptor, which either releases energy or further transfers energy to a final emitter. The acceptor concentration may range from 0.001% to 100%. The acceptor may be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, luminescence may occur from any or all of a sensitizer, an acceptor, and a final emitter.

According to another aspect, formulations comprising the compounds described herein are also disclosed.

The OLEDs disclosed herein may be included in one or more of consumer products, electronic component modules, and lighting panels. The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, while the compound may be a non-emissive dopant in other embodiments.

In yet another aspect of the present disclosure, formulations comprising the novel compounds disclosed herein are described. The formulation may include one or more components 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 disclosed herein.

The present disclosure includes any chemical structure comprising a novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. That is, a compound of the present invention, or a monovalent or polyvalent variant 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 supermacromolecules). As used herein, "monovalent variant of a compound" refers to a moiety that is identical to a compound except that one hydrogen has been removed and replaced with a bond to the remaining chemical structure. As used herein, "multivalent variant of a compound" refers to a moiety that is identical to a compound except that more than one hydrogen has been removed and a bond or bonds to the remaining chemical structure have been replaced. In the case of supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

In some embodiments, at least one of the anode, cathode, or new layer disposed over the organic light emitting layer functions as a reinforcement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively binds to the emitter material and transfers the excited state energy from the emitter material to the surface plasmon polariton in a non-radiative mode. The enhancement layer is provided within a critical distance from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radioactive decay rate constant due to the presence of the enhancement layer, and the critical distance is such that the total non-radiative decay rate constant is equal to the total radioactive decay rate. Same place as constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the reinforcement layer on the opposite side of the organic light emitting layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emissive layer from the enhancement layer but still outcouples 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 in free space as photons. In other embodiments, energy is scattered from surface plasmon modes to other modes of the device, such as, but not limited to, organic waveguide modes, substrate modes, or other waveguide modes. If energy is scattered into the non-free space mode of the OLED, other outcoupling schemes can be incorporated to extract that energy into free space. In some embodiments, one or more intervening layers may be disposed between the reinforcement layer and the outcoupling layer. Examples of intervening layer(s) 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 is present, resulting in any or all of the following: a decrease in the rate of emission, a change in the shape of the emission line, a change in the emission intensity with angle, a change in the stability of the emitter material. , changes in the efficiency of OLEDs, and reduced efficiency roll-offs of OLED devices. Placing an enhancement layer on the cathode side, the anode side, or both creates an OLED device that exploits any of the aforementioned effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, OLEDs according to the present disclosure may include any other functional layers commonly found in OLEDs.

The reinforcement layer may be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. 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 this embodiment the metal is Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys of these materials. or mixtures, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, in which the entire medium behaves differently than the sum of its material parts. In particular, the applicant defines an optically active metamaterial as a material having both a negative dielectric constant and a negative transmittance. On the other hand, the hyperbolic metamaterial is an anisotropic medium having a different sign with respect to a spatial direction with different permittivity or transmittance. Optically active metamaterials and hyperbolic metamaterials are strictly distinct from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium must appear uniformly in the direction of propagation on the wavelength-length scale of light. do. Using terms understood by one of ordinary skill in the art: the dielectric constant of a metamaterial in the direction of propagation can be described as an effective medium approximation. Plasmonic materials and metamaterials provide a way to control the propagation of light that can improve OLED performance in a variety of ways.

In some embodiments, the reinforcement layer is provided as a planar layer. In other embodiments, the reinforcement layer has features of wavelength size that are arranged periodically, quasi-periodically, or randomly, or features of subwavelength size that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features, or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features. In some embodiments, the outcoupling layer may be comprised of a plurality of nanoparticles and in other embodiments the outcoupling layer is comprised of a plurality of nanoparticles disposed over the material. Outcoupling in these embodiments comprises 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; adjustable by at least one of changing the refractive index of the material or additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcement layer, and/or changing the material of the reinforcement layer. The plurality of nanoparticles of the device are coated with a shell of a different type of material as a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack or layer of one or more materials, and/or a core of one material. It may be formed of at least one of the cores. In some embodiments, the outcoupling layer comprises: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, at least one nanoparticle selected from the group consisting of Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layers disposed thereon. In some embodiments, the polarization of light emission can be tuned using an outcoupling layer. By varying the dimension and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments the outcoupling layer also acts as an electrode of the device.

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

The materials described herein as useful for certain layers in organic light emitting devices can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those of ordinary skill in the art can readily refer to the literature to identify other materials that may be useful in combination. have.

a) Conductive dopants:

The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by creating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductive dopant and an n-type conductive 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 to be used in the present disclosure is not particularly limited, and any compound may be used as long as it is commonly used as a hole injection/transport material. Non-limiting examples of substances include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers comprising fluorohydrocarbons; polymers with conductive dopants; conductive polymers such as PEDOT/PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives such as MoO _x ; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes and crosslinkable compounds.

Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the structural formula:

each Ar ¹ to Ar ⁹ is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene the group consisting of; 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, oxadia Gin, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine , xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and aromatic heterocysts such as selenophenodipyridine. the group consisting of click compounds; and 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 cyclic group, which is the same type or a different type group selected from an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. It is selected from the group consisting of 2 to 10 cyclic structural units bonded through the above or directly bonded to each other. Each Ar may be unsubstituted or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, may be substituted with a substituent selected from the group consisting of alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, Ar ¹ to Ar ⁹ are independently selected from the group consisting of:

where k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are C (including CH) or N; Z ¹⁰¹ is NAr ¹ , O or S; Ar ¹ has the same group as defined above.

Non-limiting examples of metal complexes used in HIL or HTL include the formula:

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

In one embodiment, (Y ¹⁰¹ -Y ¹⁰² ) is a 2-phenylpyridine derivative. In another embodiment, (Y ¹⁰¹ -Y ¹⁰² ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os and Zn. In a further aspect, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V versus Fc ⁺ /Fc couple.

Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO20133018530, WO2013039073, WO20133087142, WO2013118812, WO2013120 577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.

c) EBL :

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiency and/or longer lifetime when compared to a similar device without the blocking layer. A blocking layer can also be used to confine light 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 the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in EBL contains the same molecule or functional group used as one of the hosts described below.

d) Host:

The light emitting layer of the organic EL device of the present disclosure preferably includes at least a metal complex as a light emitting material, and may include 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 the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

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

where Met is a metal; (Y ¹⁰³ -Y ¹⁰⁴ ) is a bidentate ligand, and Y ¹⁰³ and Y ¹⁰⁴ are independently selected from C, N, O, P and S; 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; k′+k″ is the maximum number of ligands that can be attached to the metal.

이며, 여기서 (O-N)은 원자 O 및 N에 배위된 금속을 갖는 2좌 리간드이다.In one embodiment, the metal complex is

where (ON) is a bidentate ligand with a metal coordinated to the atoms O and N.

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

In one aspect, the host compound is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, p Rolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine , oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, Phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenofe the group consisting of nodipyridine; and a group of the same type or a different type selected from an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group and is 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 cyclic group. It contains at least one selected from the group consisting of 2 to 10 cyclic structural units bonded through the above or directly bonded to each other. Each option within each group may be unsubstituted or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl , alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. .

In one embodiment, the host compound contains one or more of the following groups in the molecule:

wherein R ¹⁰¹ is hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; It has a similar definition to Ar. k is an integer from 0 to 20 or from 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are independently selected from C (including CH) or N. Z ¹⁰¹ and Z ¹⁰² are 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: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR2012088644, KR2012129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244,362013 WO2011081423, WO2011012 WO2014142472, US20170263869, US20160163995, US9466803,

e) additional emitter :

One or more additional emitter dopants may be used in combination with the compounds of the present disclosure. Examples of the additional emitter dopant are not particularly limited, and any compound may be used as long as it is typically used as an emitter material. Examples of suitable emitter materials include phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as type E delayed fluorescence), triplet-triplet extinction, or a combination of these processes that can cause luminescence. compounds, but are not limited thereto.

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: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155 , EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670 , US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930 , US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US2010024400 4, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US201110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US201346665653, US201365653, US20136674, US32, 2014 US6835469, US6921915, US7279704, US7332232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, WO06081973, WO06121811, WO07020018067, WO20080511, WO07020018065, WO500835571, WO2001540, WO1, WO5, 115970, WO071540, WO64 WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.

f) HBL :

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiency and/or longer lifetime when compared to a similar device without the blocking layer. A blocking layer can also be used to confine light emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (far 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 (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one embodiment, the compound used in HBL contains the same molecule or functional group used as the host described above.

In another embodiment, the compound used in HBL contains one or more of the following groups in the molecule:

where k is an integer from 1 to 20; L ¹⁰¹ is another ligand, and k' is an integer from 1 to 3.

g) ETL :

The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping can be used to improve 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 usually used to transport electrons.

In one embodiment, the compound used in ETL comprises one or more of the following groups in the molecule:

wherein R ¹⁰¹ is hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; It has a definition similar to Ar. Ar ¹ to Ar ³ have similar definitions to Ar described above. k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are selected from C (including CH) or N.

In another embodiment, metal complexes used in ETL include, but are not limited to:

wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L ¹⁰¹ is another ligand; k' is an integer value from 1 to the maximum number of ligands to which a metal can be attached.

Non-limiting examples of ETL materials that can be used in OLEDs 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, KR201330108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US201115602014, US2011210320, US2012, , WO2010067894, WO2010072300, WO20111074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

h) Majesty generative layer ( CGL ):

In a tandem or stacked OLED, CGL plays an essential role in terms of performance, which consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and the electrode. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and the anode, respectively; After that, the bipolar current gradually reaches a steady state. Common CGL materials include n and p conductive dopants used in the transport layer.

In any of the aforementioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or completely deuterated. Accordingly, any of the specifically enumerated substituents, such as, but not limited to, methyl, phenyl, pyridyl, and the like, may be in their undeuterated, partially deuterated and fully deuterated forms. Likewise, substituent types such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, and the like may also be deuterated, partially deuterated, and fully deuterated forms thereof.

It is to be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the present invention. For example, many of the materials and structures described herein may be substituted for other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may also include modifications derived from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that there is no intention to limit the various theories as to why the present invention works.

Experiment

Step 1: Synthesis of 1,2-bis(ethynyldimethylsilyl)ethane 2

Ethynylmagnesium chloride (499 mL, 250 mmol) was added to a stirred solution of 1,2-bis(chlorodimethylsilyl)ethane 1 (24 g, 111 mmol) in THF (400 mL) at 25° C. over 90 min. Instilled through cannula. Upon complete addition, the reaction was heated to 80° C. and stirred at this temperature for 24 h at which time TLC analysis (10% EtOAc/isohexane) determined complete consumption of the starting material. The reaction was _{carefully diluted with NH 4} Cl (sat., aq., 200 mL), then Et ₂ O (200 mL) was added. The layers were partitioned _{, the aqueous phase was back extracted with Et 2} O (2×200 mL) and the combined organic extracts were washed with brine (sat., aq., 200 mL) and passed through a phase separator cartridge. The crude material was concentrated directly on silica and purified by column chromatography eluting _{with 20% Et 2} O/isohexane in neat isohexane to give the title compound 2 as a yellow oil, 19.0 g, 97.7 mmol .

Step 2: Synthesis of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carbaldehyde 4

Iodine (0.50 g, 1.95 mmol) was added to a stirred suspension of zinc (1.28 g, 19.54 mmol) in _{CH 3 CN (175 mL).} The brown color disappeared over 5 minutes, leaving a gray suspension, which was stirred for an additional 45 minutes. The suspension was cooled to 5° C. and 1,2-bis(ethynyldimethylsilyl)ethane 2 (19.0 g, 98 mmol) was added over 10 min followed by 3,3-diethoxyprop-1-yne ( 19.6 mL, 137 mmol) was added over 5 min. Finally, CoBr ₂ (2.14 g, 9.77 mmol _{) was added as a solution in CH 3} CN (25 mL) over 10 min. The mixture turned brown over 20 min and it was stirred at 25° C. for 24 h, at which time TLC indicated complete consumption of the starting material. The reaction was diluted with 2N HCl (aq, 2eq., 100 mL) and stirred for 24 h, at which time the reaction was diluted with water and EtOAc. The layers were separated and the aqueous phase was back extracted with EtOAc (x2). The combined organic extracts were washed with brine (x1), dried over MgSO ₄ , concentrated directly on silica and purified by column chromatography eluting with 5% EtOAc - 10% EtOAc/isohexane in neat isohexane as an orange oil. The title compound was obtained, 11.2 g, 45.1 mmol.

Step 3: Synthesis of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carboxylic acid 5

1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carbaldehyde 4 (11.2 g, 45.1) in DMF (180 mL) mmol) and oxone (27.7 g, 90 mmol) was stirred at 25° C. for 18 h at which time TLC analysis (10% EtOAc/isohexane) indicated complete consumption of the starting material. The reaction was diluted with water and EtOAc and the phases were separated. The aqueous phase was back extracted with EtOAc (x2), the combined organic phases washed with brine (x2), passed through a phase separator cartridge and concentrated directly on silica column chromatography eluting with 25% EtOAc/isohexane in neat isohexane. to give the title compound as a white solid, 9.27 g, 35.1 mmol.

Step 4: 1,1,4,4-tetramethyl- N Synthesis of -(pivaloyloxy)-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carboxamide 6

1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carboxylic acid 5 (9.27 g, 35.1 mmol) was mixed with THF (350 mL) and the solution was cooled to 0 °C. 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide (T3P, 50% in EtOAc, 45.9 mL, 77 mmol) Dropwise over 5 min, the reaction stirred at 25° C. for 90 min, then DIPEA (36.6 mL, 210 mmol) and O -pivaloylhydroxylaminetrifluoromethanesulfonate 12 (10.30 g, 38.6 mmol) were added were added successively. The reaction was stirred for 20 h at which time TLC analysis indicated complete consumption of the starting material. The reaction was diluted with water and EtOAc, and the layers were separated. The aqueous phase was back extracted with EtOAc (x1) and the combined organic extracts _{were washed with NaHCO 3} (sat., aq. x1) and brine (sat., x1), then passed through a phase separator and concentrated directly on silica. Purification by column chromatography eluting with 10% EtOAc - 25% EtOAc/isohexane in neat isohexane afforded the title compound as a waxy yellow solid, 7.53 g, 95% purity, 19.67 mmol.

Step 5: of 1,1,4,4-tetramethyl-2,3,4,7-tetrahydro-[1,4]disilino[2,3-g]isoquinolin-6(1H)-one 8 synthesis

1,1,4,4-tetramethyl- N- (pivaloyloxy)-1,2,3,4-tetrahydrobenzo[b][1,4]disilin-6-carboxamide 6 (7.53 g, 19.67 mmol), vinyl acetate (2.72 mL, 29.5 mmol), CsOAc (1.13 g, 5.90 mmol) and dichloro(pentamethylcyclopentadienyl)rhodium(II) dimer (0.13 g, 0.20 mmol) were combined and MeOH was dissolved in The reaction was vacuum/nitrogen backfilled to reflux (x3) and then heated at 45° C. for 21 h at which time TLC analysis indicated complete consumption of the starting material. The reaction was concentrated directly on silica and purified by column chromatography eluting with 25%-50% EtOAc/isohexane in neat isohexane to afford the title compound as a yellow solid, 3.49 g, 12.1 mmol.

Step 6: Synthesis of 6-chloro-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilino[2,3-g]isoquinoline 9

1,1,4,4-tetramethyl-2,3,4,7-tetrahydro-[1,4]disilino[2,3-g]isoquinolin-6(1H)-one 8 (3.49 g, 12.1 mmol) was dissolved in POCl ₃ (11.4 mL, 122 mmol) and Et ₃ N (1.7 mL, 12.1 mmol) was added at 25° C. The reaction mixture was sparged with nitrogen for 5 minutes, then heated to 85° C. and stirred at this temperature for 75 minutes. The reaction was concentrated in vacuo and the crude product was combined with the crude material (2.3 g, 8.0 mmol) from another reaction performed in parallel. The combined crude material was dissolved in EtOAc (200 mL) and water (200 mL) was added. The phases were separated and the aqueous phase was back extracted with EtOAc (2 x 100 mL). The combined organic phases were washed with brine (2 x 100 mL), passed through a phase separator cartridge and concentrated directly on silica. Purification by column chromatography in neat isohexane eluting with 10% EtOAc/isohexane gave the title compound as an orange oil, 5.56 g, 18.2 mmol (91% total yield).

Step 7: 6-(3,5-Dimethylphenyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilino[2,3-g] Synthesis of isoquinoline

6-Chloro-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilino[2,3-g]isoquinoline 9 (5.56 g, 18.2 mmol) , (3,5-dimethylphenyl) boronic acid (3.27 g, 21.8 mmol), Pd tetra-triphenylphosphine (1.05 g, 0.91 mmol) and _{K 2 CO 3 (10.05 g,} 72.7 mmol) blended with THF (60 a mL) and water (60 mL). The reaction mixture was sparged with nitrogen for 15 minutes and then vacuum-nitrogen backfilled to reflux (x5). The reaction was heated to 80° C. and stirred at this temperature for 18 h. The reaction was cooled to 25° C. and diluted with EtOAc and water. The phases were separated and the aqueous phase was back extracted with EtOAc (x1). The combined organic extracts were washed with brine (x1), passed through a phase separator and concentrated directly on silica. Purification by column chromatography in neat isohexane eluting with 5% - 10% EtOAc/isohexanes gave the title compound as a pale yellow oil, which was slowly recrystallized under high vacuum as a pale yellow solid, 5.63 g, 15.0 mmol .

6-(3,5-dimethylphenyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilino[ in a mixture of 2-ethoxyethanol and water A suspension of 2,3-g]isoquinoline (0.17 g, 0.45 mmol) and iridium(III) chloride hydrate (75 mg, 0.21 mmol) was heated at 100° C. overnight to obtain the intermediate μ -dichloride complex (0.3 g 72% ) was obtained.

Intermediate μ -dichloride complex (70 mg, 0.036 mmol), 3,7-diethylnonane-4,6-dione (46 mg, 0.215 mmol), powdered potassium carbonate (30 mg, 0.215 mmol) were added to THF and , the reaction mixture was heated at 50 °C overnight. The reaction mixture was cooled to room temperature and DIUF water (500 mL) was added. The slurry was filtered and the solvent was removed. The residue was coated on silica gel and purified on a silica gel column, eluting with a gradient of a mixture of dichloromethane and hexane to give the present compound (30 mg, 36% yield) as a red solid.

A suspension of 1-(3,5-dimethylphenyl)-6-(trimethylsilyl)isoquinoline (6.53 g, 21.37 mmol, 2.2 equiv) and iridium(III) chloride hydrate (2.9 g, 9.71 mmol, 1.0 equiv) was prepared by 125 The intermediate μ -dichloride complex was obtained by heating at °C overnight. The reaction mixture was cooled to room temperature. 3,7-diethylnonane-4,6-dione (2.06 g, 9.71 mmol, 2.0 equiv), powdered potassium carbonate (2.02 g, 14.58 mmol, 3.0 equiv) and triethylphosphate (60 mL) were added and the reaction mixture was heated at 42° C. overnight. The reaction mixture was cooled to room temperature and DIUF water (500 mL) was added. The slurry was filtered and the solid was washed with methanol (100 mL). The red solid was dissolved in dichloromethane (250 mL) and adsorbed onto silica gel (100 g), eluting with a gradient of 5-40% dichloromethane in hexanes on an Interchim automated chromatography system (330 g Sorbtech silica gel cartridge). bis[1-(3,5-dimethylphenyl)-2'-yl)-6-(trimethylsilyl)isoquinolin-1'-yl]-(3,7-diethyl-4, 6-nonandionato- k ₂ O,O′)-iridium (III) (3.45 g, 35% yield, 99.5% purity) was obtained.

The photoluminescence (PL) spectra of both the inventive and comparative compounds are shown in FIG. 3 . The PL intensity was normalized to the maximum of the first emission peak. Both compounds exhibit a structural emission profile. The compound of the present invention exhibits a maximum peak at 639 nm with a photoluminescence photon yield (PLQY) of 86% and an excited state decay lifetime (τ) of 1.19 μs, whereas the comparative compound exhibits a peak at 636 nm with a PLQY of 85% and τ of 1.25 μs. shows the maximum peak in Although both compounds have similar emission peak maximum wavelengths, it can be seen that the intensity of the second PL peak of the compound of the present invention is lower than that of the comparative compound. The broad emission spectrum, especially the strong contribution of the second emission peak, is a major problem for achieving good color purity. In addition, the compounds of the present invention exhibit higher PLQY and shorter τ. When the compounds of the present invention are used as emissive dopants in organic electroluminescent devices, they are expected to emit more saturated red light emission with higher efficiency than comparative compounds, providing improved device performance.

Claims (20)

_A compound comprising a ligand L A of formula (I):

here:
A ¹ and A ² is each independently a monocyclic or polycyclic fused ring system comprising at least one fused or unfused 5- or 6-membered carbocyclic or heterocyclic ring;
And X ¹ -X ⁴ are each independently C or N, stage, at least one of X ¹ -X ⁴ is C, X ¹ -X ^4, at least one of which is N;
K ¹ and each K ² is independently selected from the group consisting of a direct bond, O, and S;
L ¹ is selected from the group consisting of a single bond, O, S, C=R', CR'R", SiR'R", GeRR', BR', BR'R", and NR';
R ^A and each R ^D represents unsubstituted, monosubstituted, or up to the maximum permissible substitution for its related ring;
R ^A and At least one of R ^{D is the corresponding A 1} and has the structure of formula II fused to A ^{2 :}

;
Z ¹ -Z ⁴ are each independently selected from the group consisting of CRR', SiRR', and GeRR', with the proviso ^{that at least one of Z 1} -Z ⁴ is GeRR' or SiRR';
n = 0 or 1;
n is 1 and A ¹ or when A ² is a pyridine ring fused to Formula II, ^{at least two of Z 1} -Z ⁴ are GeRR′ or SiRR′;
each R ^A , R ^D , R , and R′ is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof a substituent selected from the group consisting of;
Ligand L _A forms a complex with metal M via the dashed line to form a 5-membered chelate ring;
M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;
M may be coordinated to another ligand;
L _A can be linked to another ligand to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
Any two adjacent R ^A , R ^D , R , and R′ may be joined or fused to form a ring. A compound according to claim 1 comprising a ligand L _A of formula IV:

wherein ring A ¹ , ring A ² , X ¹ -X ⁴ , R ^A and R ^D is as defined herein. The compound of claim 1 , wherein each R ^A , R ^D , R , and R′ is independently hydrogen or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, A compound that is a substituent selected from the group consisting of cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof. The method of claim 1 , wherein A ¹ and one of A ² is benzene, A ¹ and The ^{other one of A 2} is selected from the group consisting of pyrimidine, pyridine, pyridazine, triazine, pyrazine, benzene, imidazole, pyrazole, oxazole, thiazole, and N-heterocyclic carbene . 2 . The remainder of claim 1 , wherein ^{one of Z 1} -Z ⁴ is SiRR′ and ^{the remainder of Z 1} -Z ⁴ is CRR′, or ^{two of Z 1} -Z ⁴ are SiRR′ and the remainder of ^{Z 1} -Z ^{4 .} is CRR'. The compound of claim 1 , wherein R and R′ are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. The compound of claim 1 , wherein the ligand L _A is selected from the group consisting of:

here:
T is selected from the group consisting of B, Al, Ga, and In;
each of Y ¹ to Y ¹³ is independently selected from the group consisting of carbon and nitrogen;
Y' is selected from the group consisting _{of BR e} , NR _e , PR _e , O, S, Se, C=O, S=O, SO ₂ , CR _e R _f , SiR _e R _f , and GeR _e R _{f ;} ;
R _e and R _f may be fused or joined to form a ring;
each R _a , R _b , R _c , and R _d independently represents unsubstituted, monosubstituted, or up to the maximum permissible number of substitutions for its associated ring;
R _a1 , R _b1 , R _c1 , R _d1 , R _a , R _b , R _c , R _d , R _e and each of R _f is independently hydrogen, or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl , aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; a substituent selected from the group consisting of general substituents as defined herein;
any two adjacent R _a , R _b , R _c , R _d , R _e and R _f may be fused or joined to form a ring or a polydentate ligand. The compound of claim 1 , wherein Formula II is selected from the group consisting of:

wherein R, R' may form a ring; R and R' are selected from the group consisting of:

The compound of claim 1 , wherein the ligand L _A is selected from the group consisting of the following ligands:

where i is an integer from 1 to 688, and for each i , R ^E and G is defined in Table 1 below:

wherein R ¹ to R ⁴³ have the following structure:

G ¹ to G ²² have the structure:

The method of claim 1, wherein the compound has the formula M (L _{A) x} (L _{B) y (C} L) _z, wherein L and _B each L _C is a bidentate ligand; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x + y + z is the oxidation state of the metal M compound. 11. The method of claim 10, wherein the one L _B is selected from the group consisting of compounds the formula:

here:
T is selected from the group consisting of B, Al, Ga, and In;
Y ¹ to Y ¹³ are each independently selected from the group consisting of carbon and nitrogen;
Y' is selected from the group consisting _{of 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 ;} ; where R _e and R _f may be fused or joined to form a ring;
each of R _a , R _b , R _c , and R _d may independently represent unsubstituted, mono-substituted, or up to the maximum permissible substitution for its associated ring;
each R _a , R _b , R _c , R _d , R _e R _f , R _a1 , R _b1 , R _c1 , R _d1 is independently hydrogen, or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aryl Alkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sul a substituent selected from the group consisting of phinyl, sulfonyl, phosphino, and combinations thereof;
Two adjacent substituents of R _a , R _b , R _c , and R _d may, where chemically possible, be fused or joined to form a ring or a polydentate ligand. 11. The compound of claim 10, wherein L _C is a substituted or unsubstituted acetylacetonate ligand. 10. The method of claim 9 wherein the compound of the general formula _{Ir (L A i - m)} 3 Ir based on (L _{A 1 - 1) 3} to Ir (L _{A688-68) 3,} the formula Ir (L _{A i - m)} (L _{B k) 2} Ir based on _{(L a 1 - 1) (} L B 1) 2 to _{Ir (L A688-68) (L B} 270) 2, the formula _{Ir (L a i - m)} 2 (L _{1) 2 (L C 1-} i) to _{Ir (L A688-68) 2 (L} C 1416-i) and general formula _{Ir (L a i - - Ir} (L a 1 , based on _{C jI) m) 2} ( _{L C j-II) Ir (} L a 1 , based on _{- 1) 2 (L C 1} -II) to Ir (L _{A688-68) 2} (is selected from the group consisting of _{C 1416 L-II),} where i is is 1 to 688 integer, m is an integer from 1 to 68, k is 1 to 270 and integer, j is an integer from 1 to 1416, L _B1 to L _B270 has the following structure:

L _C1-I to L _C1416-I is

Based on the structure of, L _C1-II to L _C1416-II are

Based on the structure of L _{C j -I} and In the L _{j -II C} for each _{C j} L, R ²⁰¹ and R ²⁰² is each independently defined in the table below:

A ^{compound wherein R D1} to R ^D246 have the structure:

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

2. The method of claim 1, wherein formula III:

A compound having the structure of:
here:
M ¹ is Pd or Pt;
moieties E and F are each independently a monocyclic or polycyclic ring structure comprising 5- and/or 6-membered carbocyclic or heterocyclic rings;
Z ¹ and each Z ² is independently C or N;
K ¹ , K ² , K ³ , and K ⁴ are each independently selected from the group consisting of a direct bond, O, and S, at least two of which are direct bonds;
L ¹ , L ² , L ³ and each L ⁴ is independently selected from the group consisting of a single bond, no bond, O, S, CR'R", SiR'R", BR', and NR', L ¹ , L ² , L ³ and at least 3 of L ^{4 are present;}
R ^E and each R ^F independently represents unsubstituted, monosubstituted, or up to the maximum permissible number of substitutions for its related ring;
each of R′, R″, R ^E , and R ^F is independently hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl , a substituent selected from the group consisting of heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;
two adjacent R ^A , R ^D , R ^E , and R ^F , where chemically possible, may be joined together or fused together to form a ring;
X ¹ -X ⁴ , R ^A , R ^D and ring A ¹ and A ² is all defined in the same manner as above. 16. A compound according to claim 15 selected from the group consisting of:

here:
R ^x and each R ^y is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
R ^G at each occurrence is independently hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, hetero a substituent selected from the group consisting of aryl, nitrile, isonitrile, sulfanyl, and combinations thereof;
X ¹ -X ⁴ , R ^A , R ^D and ring A ¹ and A ² is all defined in the same manner as above. anode;
cathode; and
organic layer disposed between the anode and cathode
An organic light emitting device (OLED) comprising:
An OLED wherein the organic layer comprises a compound comprising a _{ligand L A} of formula (I):

here:
A ¹ and A ² is each independently a monocyclic or polycyclic fused ring system comprising at least one fused or unfused 5- or 6-membered carbocyclic or heterocyclic ring;
And X ¹ -X ⁴ are each independently C or N, stage, at least one of X ¹ -X ⁴ is C, X ¹ -X ^4, at least one of which is N;
K ¹ and each K ² is independently selected from the group consisting of a direct bond, O, and S;
L ¹ is selected from the group consisting of a single bond, O, S, C=R', CR'R", SiR'R", GeRR', BR', BR'R", and NR';
R ^A and each R ^D represents unsubstituted, monosubstituted, or up to the maximum permissible substitution for its related ring;
R ^A and At least one of R ^{D is the corresponding A 1} and has the structure of formula II fused to A ^{2 :}

;
Z ¹ -Z ⁴ are each independently selected from the group consisting of CRR', SiRR', and GeRR', with the proviso ^{that at least one of Z 1} -Z ⁴ is GeRR' or SiRR';
n = 0 or 1;
n is 1 and A ¹ or when A ² is a pyridine ring fused to Formula II, ^{at least two of Z 1} -Z ⁴ are GeRR′ or SiRR′;
each R ^A , R ^D , R , and R′ is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof a substituent selected from the group consisting of;
Ligand L _A forms a complex with metal M via the dashed line to form a 5-membered chelate ring;
M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;
M may be coordinated to another ligand;
L _A can be linked to another ligand to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
Any two adjacent R ^A , R ^D , R , and R′ may be joined or fused to form a ring. 18. The method of claim 17, wherein the organic layer further comprises a host, wherein the host is triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-di An OLED comprising at least one chemical group selected from the group consisting of benzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. 18. The OLED of claim 17, wherein the host is selected from the group consisting of the following compounds and combinations thereof:

anode;
cathode; and
organic layer disposed between the anode and cathode
A consumer product comprising an organic light emitting device (OLED) comprising: wherein the organic layer comprises a compound comprising a _{ligand L A of formula (I):}

here:
A ¹ and A ² is each independently a monocyclic or polycyclic fused ring system comprising at least one fused or unfused 5- or 6-membered carbocyclic or heterocyclic ring;
And X ¹ -X ⁴ are each independently C or N, stage, at least one of X ¹ -X ⁴ is C, X ¹ -X ^4, at least one of which is N;
K ¹ and each K ² is independently selected from the group consisting of a direct bond, O, and S;
L ¹ is selected from the group consisting of a single bond, O, S, C=R', CR'R", SiR'R", GeRR', BR', BR'R", and NR';
R ^A and each R ^D represents unsubstituted, monosubstituted, or up to the maximum permissible substitution for its related ring;
R ^A and At least one of R ^{D is the corresponding A 1} and has the structure of formula II fused to A ^{2 :}

;
Z ¹ -Z ⁴ are each independently selected from the group consisting of CRR', SiRR', and GeRR', with the proviso ^{that at least one of Z 1} -Z ⁴ is GeRR' or SiRR';
n = 0 or 1;
n is 1 and A ¹ or when A ² is a pyridine ring fused to Formula II, ^{at least two of Z 1} -Z ⁴ are GeRR′ or SiRR′;
each R ^A , R ^D , R , and R′ is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof a substituent selected from the group consisting of;
Ligand L _A forms a complex with metal M via the dashed line to form a 5-membered chelate ring;
M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;
M may be coordinated to another ligand;
L _A can be linked to another ligand to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
Any two adjacent R ^A , R ^D , R , and R′ may be joined or fused to form a ring.

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