CN112079869A - Organic electroluminescent material and device - Google Patents

Abstract

The present application relates to organic electroluminescent materials and devices. Organometallic compounds are provided. Formulations comprising these organometallic compounds are also provided. Also provided are OLEDs and related consumer products utilizing these organometallic compounds.

Description

Organic electroluminescent material and device

CROSS-REFERENCE TO RELATED APPLICATIONS

Priority of the present application for united states provisional application No. 63/000,585 filed 3/27/2020 and No. 62/861,560 filed 6/14/2019, which are hereby incorporated by reference in their entirety, is claimed at 35u.s.c. § 119 (e).

Technical Field

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

Background

Photovoltaic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, and therefore organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for particular 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 may have performance advantages over conventional materials.

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

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

Disclosure of Invention

In one aspect, the present disclosure provides a ligand L comprising formula I_AThe compound of (1):

wherein X is independently C or N; z¹And Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C; ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring; r^A、R^B、R^CAnd R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring; r^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two substituents may be linked or fused to form a ring, wherein the ligand L_AComplexed to metal M via two indicated dotted lines; wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag and Au,and can coordinate with other ligands; and wherein the ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

In another aspect, the present disclosure provides a ligand L comprising formula I as described herein_AA formulation of the compound of (1).

In another aspect, the present disclosure provides an OLED having an organic layer containing a ligand L comprising formula I as described herein_AThe compound of (1).

In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a ligand L comprising formula I as described herein_AThe compound of (1).

Drawings

Fig. 1 shows an organic light emitting device.

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

Detailed Description

A. Term(s) for

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

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

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

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

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

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

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

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

The term "acyl" refers to a substituted carbonyl group (C (O) -R_s)。

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

The term "ether" means-OR_sA group.

The terms "thio" or "thioether" are used interchangeably and refer to-SR_sA group.

The term "sulfinyl" refers to-S (O) -R_sA group.

The term "sulfonyl" refers to-SO₂-R_sA group.

The term "phosphino" refers to-P (R)_s)₃Group, wherein each R_sMay be the same or different.

The term "silyl" refers to-Si (R)_s)₃Group, wherein each R_sMay be the same or different.

The term "oxyboronyl" refers to-B (R)_s)₂Group or Lewis adduct thereof (R) -B (R)_s)₃Group, wherein R_sMay be the same or different.

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

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

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

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

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

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

The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. In addition, the aralkyl group may be optionally substituted.

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

The term "aryl" refers to and includes monocyclic aromatic hydrocarbon radicals and polycyclic aromatic ring systems. Polycyclic rings can have two or more rings in which two carbons are common to two adjoining rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbyl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryls, heterocyclics, and/or heteroaryls. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Especially preferred are aryl groups having six carbons, ten carbons, or twelve carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, perylene,

Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, Si and Se. In many cases O, S or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic with 5 or 6 ring atoms, and rings may have one to six heteroatoms. A heteropolycyclic system can have two or more rings in which two atoms are common to two adjoining rings (the rings are "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryls, heterocycles and/or heteroaryls. The heterocyclic aromatic ring system may have one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, benzothienopyridine, and selenenopyridine, preferably dibenzothiophene, and benzothiophene, Dibenzofurans, dibenzoselenophenes, carbazoles, indolocarbazoles, imidazoles, pyridines, triazines, benzimidazoles, 1, 2-azaborines, 1, 3-azaborines, 1, 4-azaborines, borazines, and aza analogs thereof. In addition, 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, triazine, and benzimidazole are of particular interest, as well as their respective corresponding aza analogues.

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

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

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

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

In other cases, more preferred general substituents are selected from the group consisting of: deuterium, fluoro, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, e.g., carbon or nitrogen. For example, when R is¹When representing a single substitution, then one R¹Must not be H (i.e., substituted). Similarly, when R is¹When representing disubstituted, then two R¹Must not be H. Similarly, when R is¹When represents zero or no substitution, R¹For example, it may be hydrogen of available valency for the ring atoms, such as the carbon atom of benzene and the nitrogen atom of pyrrole, or it may be hydrogen of only zero for ring atoms having fully saturated valency, such as the nitrogen atom of pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valences in the ring atoms.

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

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

As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US 2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium substituted organometallic complexes. With further reference to \37154min (Ming Yan) et al, Tetrahedron (Tetrahedron)2015,71,1425-30 and azrote (Atzrodt) et al, german applied chemistry (angelw. chem. int. ed.) (review) 2007,46,7744-65, which are incorporated by reference in their entirety, describe efficient routes for deuteration of methylene hydrogens in benzylamines and replacement of aromatic ring hydrogens with deuterium, respectively.

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

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

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a ligand L comprising_AThe compound of (1):

formula I

Wherein:

x is independently C or N; z¹And Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C; ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring; r^A、R^B、R^CAnd R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring; r^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a general substituent as described herein; and any two substituents may be linked or fused to form a ring, wherein the ligand L_AComplexed to metal M via two indicated dotted lines; wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and is

Wherein the ligand L_ACan be combined with other ligandsLinked to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments, at least one of rings a through D is a 6-membered ring and at least one of rings a through D is a 5-membered ring. In some embodiments of the compound, L_AMay be selected from the group consisting of: a ligand of formula I wherein both rings a and B are 6 membered rings; a ligand of formula I wherein both rings B and C are 6 membered rings; a ligand of formula I wherein both rings B and D are 6 membered rings; and ligands of formula I wherein both rings C and D are 5 membered rings. In some embodiments, each ring a-D is aromatic.

In some embodiments, ligand L_ACan have the structure of formula I

Wherein X⁴、X⁵And X⁶Each independently is C or N; and the rest are the same as previously defined.

In some embodiments, R^A、R^B、R^CAnd R^DEach of which may be independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some embodiments, ring a can be a 6-membered aromatic ring. In some embodiments, ring D can be a 5-membered aromatic ring. In some embodiments, both ring D and ring C can be 5-membered aromatic rings. In some embodiments, ring a can be a 6-membered aromatic ring, and both ring C and ring D can be a 5-membered aromatic ring. In some embodiments, both ring D and ring C can be aromatic. In some embodiments, ring a, ring B, ring C, and ring D can each independently be an aromatic ring. In some embodiments, X may be C.

In some embodiments, the metal M may be Pt, Ir, or Pd.

In some embodiments, ligand L_AHaving the structure of formula IA:

wherein:

X¹、X²and X³Each of which is independently C or N;

Y¹and Y²Each of which is independently selected from the group consisting of: o, S, Se, CRR ', BR, SiRR' and NR;

each of R and R' is independently hydrogen or a substituent selected from the group consisting of the general substituents as described herein;

the remaining variables are the same as defined previously, and

any two substituents may be linked or fused together to form a ring.

In some of the above embodiments, R^AAnd R^BEach of which may be independently hydrogen or a substituent selected from the group consisting of the preferred general substituents as described herein.

In some of the above embodiments, the ligand L_AaMay be linked to one or two other ligands to form a tridentate or tetradentate ligand. In some of the above embodiments, R^AAnd R^BAt least one of which may be a 5-or 6-membered aromatic ring. In some of the above embodiments, R^AAnd R^BAt least one of which may be selected from the group consisting of: benzene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, pyrazole, triazole and N-heterocyclic carbenes.

In some of the above embodiments, X¹To X⁶May each independently be C. In some of the above embodiments, X¹To X⁶May be N. In some of the above embodiments, two R^AThe substituents may be linked together to form a fused six-membered carbocyclic or heterocyclic ring. In some of the above embodiments, two R^BThe substituents may be linked together to form a fused six-membered carbocyclic or heterocyclic ring. In some of the above embodiments, Z¹And Z²May each be C. In some of the above embodiments, Z¹And Z²May each be N. In some of the above embodiments, Z¹Can be N, and Z²May be C.

In some of the above embodiments, each Y¹And Y²May be independently selected from the group consisting of: o, S, CRR' and NR. In some of the above embodiments, Y¹And Y²May be all O. In some of the above embodiments, Y¹And Y²May both be CRR'. In some of the above embodiments, Y¹And Y²May all be S. In some of the above embodiments, M may be Ir or Pt.

In some of the above embodiments, the ligand L_AMay be selected from the group consisting of:

wherein:

Y¹and Y²Each independently selected from the group consisting of: o, S, CRR ', BR, SiRR', and NR;

R¹and R²Each represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R¹and R²Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

any two substituents may be connected or fused to form a ring; and is

The remaining variables are the same as previously defined.

In some of the above embodiments, wherein the ligand L_AHaving the structure of formula IA, ligand L_AIs optionally selected from L_Aai-jGroup of (I) wherein i is 1An integer of to 19, j is an integer of 1 to 126; wherein for each i, L_Aai-jHas a structure defined as:

wherein for each j, R¹、R²、Y¹And Y²As defined in table 1 below:

in some embodiments, ligand L_AMay be selected from the group consisting of:

formula IB-1

And formula IB-2

Wherein:

X²⁰and X²¹Each of which is independently C or N;

the remaining variables are the same as previously defined; and is

Any two substituents may be connected or fused to form a ring.

In some of the above embodiments, R^A、R^B、R^CAnd R^DEach of which may be independently hydrogen or a substituent selected from the group consisting of the preferred general substituents as defined herein.

In some of the above embodiments, X²⁰And X²¹May each independently be C. In some of the above embodiments, ring D may be a 5-membered ring. In some of the above embodiments, ring D may be a furan or thiophene ring. In some of the above embodiments, ring a may be a 6-membered ring. In some of the above embodiments, ring a may be a benzene ring. In some of the above embodiments, ring a may be a 5-membered ring. In some of the above embodiments, the ring may be a furan, thiophene, imidazole, isoxazole, or isothiazole ring. In some of the above embodiments, ring D and ring C may both be aromatic rings. In some of the above embodiments, ring a, ring B, ring C, and ring D may all be aromatic rings.

In some of the above embodiments, Z²Can be N, and Z¹May be C. In some of the above embodiments, Z¹Can be N, and Z²May be C. In some of the above embodiments, X⁴、X⁵And X⁶Each of which may independently be C.

In some of the above embodiments, two adjacent R^AThe substituents are joined to form a fused ring. In some of the above embodiments, two adjacent R^BSubstituents may be joined to form fused rings. In some of the above embodiments, two adjacent R^CSubstituents may be joined to form fused rings. In some of the above embodiments, two adjacent R^DSubstituents may be joined to form fused rings. In these embodiments, the fused ring may be a 6-membered aromatic ring.

In some of the above embodiments, R^A、R^B、R^COr R^DOne of which can be D, F, alkyl, cycloalkyl, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R^DAnd R^CCannot be joined to form a ring.

In some of the above embodiments, M may be Ir or Pt.

In some of the above embodiments, the compound may further comprise at least one substituted or unsubstituted phenylpyridine ligand. In some of the above embodiments, the compound may further comprise at least one substituted or unsubstituted acetylacetonate ligand.

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

in some of the above embodiments, wherein the ligand L_AA ligand L selected from the group consisting of formula IB-1 and formula IB-2_ACan be selected from the group consisting of table 2 below:

wherein the content of the first and second substances,

Y¹selected from the group consisting of: o, S, CRR ', BR, SiRR', and NR;

R¹and R²Each represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R¹and R²Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is

Any two substituents may be connected or fused to form a ring.

In some of the above embodiments, wherein the ligand L_AA ligand L selected from the group consisting of formula IB-1 and formula IB-2_AIs optionally selected from L_Abp-lWherein p is an integer from 1 to 16, l is an integer from 1 to 189; wherein for each p, L_Abp-lHas a structure defined as:

wherein for each l, R¹、R²And Y¹As defined in table 3 below:

in some embodiments, ligand L_AHas the following structure:

formula IC

Wherein:

one is a single bond and the other is a double bond;

G¹n or CR when in double bond, or O, NR or CRR' when in single bond;

G²n or CR when in double bond, or O, NR or CRR' when in single bond;

the remaining variables are the same as previously defined; and is

Any two substituents may be connected or fused to form a ring.

In some of the above embodiments, R^AAnd R^BEach of which may be independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some of the above embodiments, ring a may be a 6-membered ring. In some of the above embodiments, ring a may be a benzene ring. In some of the above embodiments, Z²Can be N, and Z¹May be C. In some of the above embodiments, Z¹Can be N, and Z²May be C. In some of the above embodiments, X⁴、X⁵And X⁶Each of which may independently be C.

In some of the above embodiments, two adjacent R^ASubstituents may be joined to form fused rings. In some of the above embodiments, two adjacent R^BSubstituents may be joined to form fused rings. In these embodiments, the fused ring may be a 6-membered aromatic ring.

In some of the above embodiments, R may be alkyl, cycloalkyl, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, M may be Pt.

In some of the above embodiments, wherein the ligand L_AHaving the structure of formula IC, ligand L_AMay be selected from the group consisting of:

wherein all variables are the same as previously defined.

In some of the above embodiments, wherein the ligand L_AHaving the structure of formula IC, ligand L_AIs optionally selected from L_ACm-nWherein m is an integer from 1 to 27, and n is an integer from 1 to 40, wherein for each m, L_Acm-nHas a structure defined as:

wherein for each n, R¹And R²The definition is as follows:

in some of the embodiments, the compound may have the formula M (L)_A)_x(L_B)_y(L_C) Wherein L is_BAnd L_CEach is a bidentate ligand; and wherein x is 1,2 or 3; y is 1 or 2; z is 0, 1 or 2; and x + y + z is the oxidation state of metal M.

In some of the embodiments, the compound may have a formula selected from the group consisting of: ir (L)_A)₃、Ir(L_A)(L_B)₂、Ir(L_A)₂(L_B) And Ir (L)_A)(L_B)(L_C) (ii) a And wherein L_A、L_BAnd L_CAre different from each other.

In some of the embodiments, the compound may have the formula Pt (L)_A)(L_B) Wherein L is_AAnd L_BMay be the same or different. In some of the embodiments, L_AAnd L_BCan be linked to form a tetradentate ligand. In some of the embodiments, L_AAnd L_BCan be linked at two places to form a macrocyclic quadridentate ligand.

In some of the embodiments, L_BAnd L_CMay each be independently selected from the group consisting of:

wherein: each Y¹'、Y²' and Y³To Y¹³Independently selected from the group consisting of carbon and nitrogen;

y' is selected from the group consisting of: BR (BR)_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_fAnd GeR_eR_f；

R_eAnd R_fMay be fused or linked to form a ring; r_a、R_b、R_cAnd R_dEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; r_a、R_b、R_c、R_d、R_eAnd R_fEach of which is independently hydrogen or a substituent selected from the group consisting of the general substituents as described herein; and R is_a、R_b、R_cAnd R_dAny two adjacent substituents of (a) may be fused or linked to form a ring or form a multidentate ligand.

In some of the embodiments, wherein the compound has a formula selected from the group consisting of: ir (L)_A)₃、Ir(L_A)(L_B)₂、Ir(L_A)₂(L_B) And Ir (L)_A)(L_B)(L_C) (ii) a And wherein L_A、L_BAnd L_CDifferent from each other, L_BAnd L_CMay each be independently selected from the group consisting of table 4 below:

wherein:

R_a' and R_b' each independently represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R_a、R_b、R_c、R_a' and R_bEach of' is independently hydrogen or a substituent selected from the group consisting of the general substituents as described herein; and is

R_a' and R_bTwo adjacent substituents of' may be fused or linked to form a ring or form a multidentate ligand.

In some of the embodiments, the compound may have the formula Ir (L)_A)₃Ir of the formula_A)(L_Bk)₂Or formula Ir (L)_A)₂(L_Bk) Wherein k is an integer of 1 to 263, wherein L_AA structure having formula I, formula IA, formula IB-1, formula IB-2, or formula IC as described herein; and each L_BkHaving the structure as defined in table 5 as described herein.

In some of the embodiments, the compound may have the formula Ir (L)_Aai-j)₃Ir of the formula_Aai-j)(L_Bk)₂Or formula Ir (L)_Aai-j)₂(L_Bk) Wherein k is an integer of 1 to 263, wherein L_Aai-jThe structures of (a) are as described herein; and each L_BkHaving the structure as defined in table 5 as described herein.

In some of the embodiments, the compound may have the formula Ir (L)_Aabp-l)₃Ir of the formula_Abp-l)(L_Bk)₂Or formula Ir (L)_Abp-l)₂(L_Bk) Wherein k is an integer of 1 to 263, wherein L_Abp-lEach L is as described herein, and_Bkhaving the structure as defined in table 5 as described herein.

In some embodiments, the compound may be selected from the group consisting of: a compound-Aa-1-1 to a compound-Aa-19-126 having a structure corresponding to each formula Ir (L)_Aai-j)₃Compound of general numbering of (a) -Aa-i-j; the compound-Ba-1-1-1 through the compound-Ba-19-126-263, which have a structure corresponding to each of the formulas Ir (L)_Aai-j)(L_Bk)₂Compound of general numbering of (1) -Ba-i-j-k; the compound-Ca-1-1-1 to the compound-Ca-19-126-263 which has a structure corresponding to each of the formulas Ir (L)_Aai-j)₂(L_Bk) Compound of general numbering of (1) -Ca-i-j-k; wherein i is an integer from 1 to 19; wherein j is an integer from 1 to 126; wherein k is an integer from 1 to 263; wherein structure L_Aai-jEach of which is a ligand of formula IA as described herein; wherein each L_BkHaving the structure as defined in table 5 as described herein.

In some of the embodiments, the compound may have the formula Ir (L)_Abp-l)₃Ir of the formula_Abp-l)(L_Bk)₂Or formula Ir (L)_Abp-l)₂(L_Bk) Wherein p is an integer from 1 to 16, L is an integer from 1 to 189, and k is an integer from 1 to 263, wherein structure L_Abp-lEach of which is a ligand of formula IB-1 or formula IB-2 as described herein; and each L_BkHaving the structure as defined in table 5 as described herein.

In some embodiments, the compound may be selected from the group consisting of: Compound-Ab-1-1 to Compound-Ab-16-189 having a structure corresponding to each of the formulae Ir (L)_Abp-l)₃Compound of general numbering formula-Ab-p-l; the compound-Bb-1-1-1 to the compound-Bb-16-189-263, which have a structure corresponding to each of the formulae Ir (L)_Abp-l)(L_Bk)₂Compound of general numbering of formula-Bb-p-l-k; the compound-Cb-1-1-1 to the compound-Cb-16-189-263, which have a structure corresponding to each of the formulas Ir (L)_Abp-l)₂(L_Bk) Compound of general numbering of (1) -Cb-p-l-k; wherein p is an integer from 1 to 16; wherein l is an integer from 1 to 189; wherein k is an integer from 1 to 263; wherein structure L_Abp-lEach as described herein; wherein each L_BkHaving the structure as defined in table 5 as described herein.

In some of the embodiments, the compound may have the formula Ir (L)_Acm-n)₃Ir of the formula_Acm-n)(L_Bk)₂Or formula Ir (L)_Acm-n)₂(L_Bk) Wherein m is an integer from 1 to 27, n is an integer from 1 to 40, and k is an integer from 1 to 263, wherein structure L_Acm-nEach of which is a ligand of formula IC as described herein; and each L_BkHaving the structure as defined in table 5 as described herein.

In some embodiments, the compound may be selected from the group consisting of: a compound-Ac-1-1 through a compound-Ac-27-40 having a structure corresponding to each of the formulas Ir (L)_Acm-n)₃Compound of general numbering formula-Acm-n; compound-Bc-1-1 to compound-Bc-27-40-263 having a structure corresponding to each formula Ir (L)_Acm-n)(L_Bk)₂Compound of general numbering formula (I) of (II-C-b-c); Compound-Cc-1-1-1 through compound-Cc-27-40-263, having a structure corresponding to each of the formulas Ir (L)_Acm-n)₂(L_Bk) Is/are as followsCompound of general numbering-Cc-m-n-k; wherein m is an integer from 1 to 27; wherein n is an integer from 1 to 40; wherein k is an integer from 1 to 263; wherein structure L_Acm-nEach as described herein; wherein each L_BkHaving the structure as defined in table 5 as described herein.

In some of the embodiments, L_BIs optionally selected from L_BkGroup, where k is an integer from 1 to 263, the structure of which is shown in table 5 below:

in some of the embodiments, L_BCan be selected from the group consisting of the structures of table 6 below: l is_B1、L_B2、L_B18、L_B28、L_B38、L_B108、L_B118、L_B122、L_B124、L_B126、L_B128、L_B130、L_B32、L_B134、L_B136、L_B138、L_B140、L_B142、L_B144、L_B156、L_B58、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_B262And L_B263。

In some of the embodiments, L_BCan be selected from the group consisting of the structures of table 6A below: l is_B1、L_B2、L_B18、L_B28、L_B38、L_B108、L_B118、L_B122、L_B124、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_B233And L_B237。

In some of the embodiments, L_BIs optionally selected from L_BBfWherein f is an integer from 1 to 180, the structure of which is shown below:

in some of the embodiments, the compound may have the structure of formula II:

wherein:

m is Pd or Pt;

ring a, ring B, ring C, ring D, ring E, and ring F are each independently a 5-or 6-membered carbocyclic or heterocyclic ring;

Z³to Z⁶Each independently is C or N;

R^Eand R^FEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring;

L¹、L²and L³Each independently is a 1 atom linking group or a 2 atom linking group, or a direct bond;

m, n and p are each independently 0 or 1, wherein m + n + p is 2 or 3;

R^Eand R^FEach of which is independently hydrogen or a substituent selected from the group consisting of the general substituents as described herein;

and any two substituents may be linked or fused together to form a ring.

In some of the above embodiments, the compound may have the structure of formula IIA

Wherein X²To X⁵Each independently is C or N;

Y¹and Y²Each of which is independently selected from the group consisting of: o, S, Se, CRR ', BR, SiRR' and NR;

x is C or N, and X is C or N,

a single bond when X is N, or a double bond when X is C, and if

Is a double bond, the other two are single bonds; and any two substituents may be linked or fused together to form a ring.

In some of the above embodiments, the compound may have the structure of formula IIB or formula IIC:

in some of the above embodiments, p can be 0, m and n can each be 1, and L¹And L²May each be independently selected from the group consisting of: direct bond, O, S, CRR ', SiRR', BR, and NR; or m can be 0, n and p can each be 1, and L²And L³May each be independently selected from the group consisting of: direct bond, O, S, CRR ', SiRR', BR, and NR. In some of the above embodiments, p can be 0, m and n can each be 1, and L¹And L²Can be a direct bond; in some of the above embodiments, m can be 0, n and p can each be 1, and L²And L³May each independently be a direct bond.

In some of the above embodiments, ring E and ring F can both be 6-membered aromatic rings. In some of the above embodiments, ring E may be a 6-membered aromatic ring and ring F may be a 5-membered aromatic ring. In some of the above embodiments, ring E and ring F can both be 5-membered aromatic rings. In some of the above embodiments, Z³And Z⁶All can be C, and Z⁴And Z⁵May be both N.

In some of the above embodiments, the compound may be selected from the group consisting of table 7 below:

wherein:

A¹to A⁸Each independently is C or N;

the maximum number of N atoms in the same ring is 3;

R^Eand R^FHaving a radical of formula (I) with R^AOr R^BThe same definition;

R^Gand R^HEach of which represents zero, single or up to the maximum permissible substitution of its associated ring;

R^Gand R^HEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

R^Xand R^YEach independently selected from the group consisting of: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

the remaining variables are the same as previously defined; and is

Any two substituents may be linked or fused together to form a ring.

In some of the above embodiments, the compound may be selected from the group consisting of compounds Pt-Si-j, where i is an integer from 1 to 13, j is an integer from 1 to 310, and for each i, the compound Pt-Si-j has a structure according to the formula shown below:

wherein for each j, Y¹、Y²、R^E、Z¹、Z²、Z⁴、Z⁴'、Z⁵And Z⁵' as defined in table 8 below:

in some of the above embodiments, the compound may be selected from the group consisting of table 9 below:

in some of the above embodiments, the compound may be selected from the group consisting of table 10 below:

in some of the above embodiments, the compound may be selected from the group consisting of table 11 below:

C. OLEDs and devices of the present disclosure

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

In some embodiments, the organic layer may contain a ligand L comprising formula I_AThe compound of (1):

wherein X is independently C or N; z¹And Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C; ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring; r^A、R^B、R^CAnd R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring; r^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a substituent as described herein; and any two substituents may be linked or fused to form a ring, wherein the ligand L_AComplexed to metal M via two indicated dotted lines; wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and wherein the ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

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

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene comprising a benzo-fused thiophene or a benzo-fused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: c_nH_2n+1、OC_nH_2n+1、OAr₁、N(C_nH_2n+1)₂、N(Ar₁)(Ar₂)、CH＝CH-C_nH_2n+1、C≡CC_nH_2n+1、Ar₁、Ar₁-Ar₂、C_nH_2n-Ar₁Or no substituent, wherein n is 1 to 10; and wherein Ar₁And Ar₂Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

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

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

and combinations thereof.

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

In some embodiments, a compound as described herein may be a sensitizer; wherein the device may further comprise a receptor; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

In yet another aspect, the OLEDs of the present disclosure can further comprise an emissive region comprising a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the emissive region may contain a ligand L comprising formula I_AThe compound of (1):

wherein X is independently C or N; z¹And Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C; ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring; r^A、R^B、R^CAnd R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring; r^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a substituent as described herein; and any two substituents may be linked or fused to form a ring, wherein the ligand L_AComplexed to metal M via two indicated dotted lines; wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and wherein the ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

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

In some embodiments, the consumer product comprises an Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain a ligand L comprising formula I_AThe compound of (1):

wherein X is independently C or N; z¹And Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C; ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring; r^A、R^B、R^CAnd R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring; r^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a substituent as described herein; and any two substituents may be linked or fused to form a ring, wherein the ligand L_AComplexed to metal M via two indicated dotted lines; wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag and Au, and can coordinate with other ligands; and wherein the ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

In some embodiments, the consumer product may be one of the following: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior lighting and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet, a phablet, a Personal Digital Assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay at a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall containing multiple displays tiled together, a theater or stadium screen, a phototherapy device, and a sign.

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

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

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

More recently, OLEDs having emissive materials that emit light from the triplet state ("phosphorescence") have been demonstrated. Baldo et al, "high efficiency Phosphorescent Emission from Organic Electroluminescent Devices" (Nature), 395, 151-154,1998 ("Baldo-I"); and baldo et al, "Very high-efficiency green organic light-emitting devices based on electrophosphorescence (Very high-efficiency green organic light-emitting devices-based on electrophosphorescence)", applied physical promo (appl. phys. lett.), volume 75, stages 3,4-6 (1999) ("baldo-II"), which are incorporated by reference in their entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.

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

More instances of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:1₄TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety.U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes comprising composite cathodes having a thin layer of a metal (e.g., Mg: Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier layers is described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer may be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

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

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

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

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

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

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

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

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

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

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

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

In some embodiments, the compounds may be used as phosphorous photosensitizers in OLEDs, where one or more layers in the OLED contain an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compounds may be used as a component of an exciplex to be used as a sensitizer. As a phosphosensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit or further transfer energy to the final emitter. The receptor concentration may range from 0.001% to 100%. The acceptor may be in the same layer as the phosphorous sensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be produced by any or all of the sensitizer, the receptor, and the final emitter.

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

The OLEDs disclosed herein can be incorporated into one or more of consumer products, 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 invention, a formulation comprising the novel compound disclosed herein is described. The formulation may include one or more of the components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

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

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

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

a) Conductive dopant:

the charge transport layer may be doped with a conductivity dopant to substantially change its charge carrier density, which in turn will change its conductivity. The conductivity is increased by the generation of charge carriers in the host 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 conductivity dopant and an n-type conductivity dopant is used in the electron transport layer.

Non-limiting examples of conductivity dopants that can be used in OLEDs in combination with the materials disclosed herein, along with references disclosing those materials, are exemplified below: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US 2012146012.

b)HIL/HTL：

The hole injection/transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is generally used as the hole injection/transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; an aromatic amine derivative; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, e.g. MoO_x(ii) a p-type semiconducting organic compounds, such as 1,4,5,8,9, 12-hexaazatriphenylhexacyano-nitrile; a metal complex; and a crosslinkable compound.

Examples of aromatic amine derivatives for use in HILs or HTLs include, but are not limited to, the following general structures:

Ar¹to Ar⁹Each of which is selected from: a group consisting of aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,

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

In one aspect, Ar¹To Ar⁹Independently selected from the group consisting of:

wherein k is an integer from 1 to 20; x¹⁰¹To X¹⁰⁸Is C (including CH) or N; z¹⁰¹Is NAr¹O or S; ar (Ar)¹Having the same groups as defined above.

Examples of metal complexes used in HILs or HTLs include, but are not limited to, the following general formulas:

wherein Met is a metal which may have an atomic weight greater than 40; (Y)¹⁰¹-Y¹⁰²) Is a bidentate ligand, Y¹⁰¹And Y¹⁰²Independently selected from C, N, O, P and S; l is¹⁰¹Is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' + k "is the maximum number of ligands that can be attached to the metal.

In one aspect, (Y)¹⁰¹-Y¹⁰²) Is a 2-phenylpyridine derivative. In another aspect, (Y)¹⁰¹-Y¹⁰²) Is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a structure comparable to Fc⁺A minimum oxidation potential in solution of less than about 0.6V for/Fc coupling.

Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein, along with references disclosing those materials, are exemplified by the following: CN102702075, DE102012005215, EP01624500, EP0169861, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091, JP 2008021621687, JP2014-009196, KR 201188898, KR20130077473, TW 201139201139402, US06517957, US 2008220158242, US20030162053, US20050123751 751, US 20060282993, US 200602872 14579, US 201181874874, US20070278938, US 20080014014464 091091091, US20080106190, US 200907192605092385, US 12460352009071794392604335200356371798, WO 20120020120020135200353141563543544354435443544354435443544354435443544354435443544354435646, WO 200200352003520035563256325632563256325646, WO 20035200352003520035200435443544354435443544354435443544354435443544354435646, WO 200605646, WO 200605632563256325632563256325646, WO 2002002002002002002002002002002002002002004356325632563256325632563256325632563256325632563256325632563256325632567, WO 2004354435443435632563256325632563256325632563256325632563243544354434354435443544354435443544354435443544354435443541, WO 200200200200200200200200200200200200200200200200200200.

c)EBL：

An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime compared to a similar device lacking a barrier layer. In addition, blocking layers can be used to limit the emission to the 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 bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

d) A main body:

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

Examples of the metal complex used as the host preferably have the following general formula:

wherein Met is a metal; (Y)¹⁰³-Y¹⁰⁴) Is a bidentate ligand, Y¹⁰³And Y¹⁰⁴Independently selected from C, N, O, P and S; l is¹⁰¹Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' + k "is the maximum number of ligands that can be attached to the metal.

In one aspect, the metal complex is:

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

In a further aspect of the present invention,met is selected from Ir and Pt. In another aspect, (Y)¹⁰³-Y¹⁰⁴) Is a carbene ligand.

In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, perylene,

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

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

wherein R is¹⁰¹Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition to Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X¹⁰¹To X¹⁰⁸Independently selected from C (including CH) or N. Z¹⁰¹And Z¹⁰²Independently selected from NR¹⁰¹O 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, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US 001446, US 20148301503, US20140225088, US2014034914, US7154114, WO2001039234, WO 2004093203203203207, WO 2005014545454545452009020090455646, WO 2002012009020120090201902019072201200907220120020190722012002012002016072201200201200201200201607246, WO 20120020120020160722012002016072201200201200201607246, WO 200201200201200201200201200201200201200201200907220020120020120020120020120020120020120090729, WO 200201200201200201200201200201200201200201200201200201200201200201200201200201200201200201200201200200200201200201200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200,

e) other emitters:

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

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein, along with references disclosing those materials, are exemplified below: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP 201207440263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US0669959, US 200100916520, US20010019782, US20020034656, US 20030068568526, US20030072964, US 2003013865657, US 200501787878788, US 20020020020020120044673, US2005123791, US 2006052449 449, US20060008670, US20060065890, US 601696, US 6016016016012006012016016310204659, US 2012002012002012002012002012000477817781979, WO 20020120020120020120020020020020020020004778177819748, US 20120020020004779, WO 200200200201200201200200200200200201200778177819748, US 20020120004779, US 20120020120020120020120020020120020020020004779, US 2002012002002002002002002002002002002002002002002002002002012000477819748, US 200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200779, US 200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200779, US 200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200200779, US 20020020020020020020020020020020020020020020020020020020120020120020020020020020020020020020020020020020020020020020020020020020020043979, US 20020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020043979, US 20020020020020020020020020020020020020020020020020020020020020020020020020020020020043979, US 20020020020120020120020020020020020020020020020020020020020020020043979, US 20020020020020020020020020020020020120020120020020020020020020020020020020020020020020020020020020020020020020020020020020120020020020020020020020020020020020020020020020043979, US 20020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020020120020120020120020120043979, US 200200200200200200200200200200200200200200200200200200200200200200200200200200200, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO 2014112450.

f)HBL：

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

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

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

wherein k is an integer from 1 to 20; l is¹⁰¹Is another ligand, and k' is an integer of 1 to 3.

g)ETL：

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

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

wherein R is¹⁰¹Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, which when aryl or heteroaryl has a similar definition to Ar described above. Ar (Ar)¹To Ar³Have similar definitions as Ar mentioned above. k is an integer of 1 to 20. X¹⁰¹To X¹⁰⁸Selected from C (including CH) or N.

In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

wherein (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atom O, N or N, N; l is¹⁰¹Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

Non-limiting examples of ETL materials that can be used in an OLED in combination with the materials disclosed herein, along with references disclosing those materials, are exemplified as follows: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US 2009017959554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US 20140142014014925, US 201401492014927, US 2014028450284580, US 5666612, US 1508431, WO 200306093060979256, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO 201107070, WO 105373, WO 201303017, WO 201314545477, WO 2014545667, WO 201104376, WO2014104535, WO 2014535,

h) charge Generation Layer (CGL)

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

In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be non-deuterated, partially deuterated, and fully deuterated forms thereof.

Experiment of

Synthesis of examples of the invention

Scheme(s)

Step 1: synthesis of 3-fluoro-2- (2-methoxynaphthalen-1-yl) -5-methylpyridine 3

In a 1L round bottom flask was charged 2-methoxynaphthalene-1-boronic acid 1(27.2g, 134.5mmol), 2-chloro-3-fluoro-5-methylpyridine 2(19.57g, 134.5mmol), and potassium carbonate (55.7g, 403.4mmol) under a nitrogen atmosphere. Dimethoxyethane (380mL) and water (90mL) were added and the resulting mixture was degassed with nitrogen for 20 minutes, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (6.85g, 5.9mmol) and degassing with nitrogen for 20 minutes. The flask was equipped with an air condenser and the mixture was heated to 95 ℃ and maintained overnight. The reaction mixture was cooled to room temperature, and ethyl acetate (approximately 600mL) and water (approximately 200mL) were added. The layers were separated and the organics were washed twice with water and brine, then MgSO₄Dried and evaporated to give a yellow oil which crystallised on standing. The crude material was purified by silica gel chromatography (on 2 cartridges of SFAR 350g HC using isohexane and ethyl acetate as eluent) to afford 3-fluoro-2- (2-methoxynaphthalen-1-yl) -5-methylpyridine 3(19.85g, 74mmol, 55% yield) as an off-white solid.

Step 2: synthesis of 9-methylnaphtho [1',2':4,5] furo [3,2-b ] pyridine DO20076

To a 3-neck 1-L round-bottom flask equipped with an air condenser was added 3-fluoro-2- (2-methoxy-1-naphthyl) -5-methylpyridine 3(19.85g, 74mmol) and pyridine hydrochloride (188g, 1627 mmol). The flask was heated at 200 ℃ for 10 hoursWhile (monitoring the reaction by LC-MS). The reaction mixture was cooled to 120 ℃, and water (approximately 300mL) was slowly added. The resulting suspension was allowed to cool to room temperature, and then the precipitate was collected by filtration. (Note that NaHCO was used)₃Saturated aqueous solution to neutralize the filtrate). The grey solid was dissolved in diethyl ether (approximately 400mL) and saturated NaHCO was used₃Water and brine, followed by MgSO₄Dried and evaporated to give a pale orange solid. Finally, this solid was wet milled with 150mL of isohexane to give 9-methylnaphtho [1',2':4,5] as a pale yellow solid]Furo [3,2-b ] s]Pyridine DO20076(11.3g, 48.1mmol, 65% yield, 99.85% purity according to Inertsil-HPLC).

And step 3: synthesis of examples of the invention

The inventive examples may be prepared by reacting the ligand from step 2 with an iridium precursor.

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

Claims (20)

1. A compound comprising a ligand L of formula I_A：

Wherein:

x is C or N;

Z¹and Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C;

ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring;

R^A、R^B、R^Cand R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R^A、R^B、R^Cand R^DEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is

Any two substituents may be connected or fused to form a ring,

wherein said ligand L_AComplexed to metal M via two indicated dotted lines;

wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and is

Wherein said ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

2. The compound of claim 1, wherein R^A、R^B、R^CAnd R^DEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

3. The compound of claim 1, wherein at least one of rings a to D is a 6-membered ring and at least one of rings a to D is a 5-membered ring.

4. The method of claim 1Compound (I) wherein L_ASelected from the group consisting of: a ligand of formula I wherein both rings a and B are 6 membered rings; a ligand of formula I wherein both rings B and C are 6 membered rings; a ligand of formula I wherein both rings B and D are 6 membered rings; and ligands of formula I wherein both rings C and D are 5 membered rings.

5. The compound of claim 1, wherein each ring a-D is an aromatic ring.

6. The compound of claim 1, wherein the metal M is Pt, Ir, or Pd.

7. The compound of claim 1, wherein the ligand L_ASelected from the group consisting of:

wherein:

X¹、X²、X³、X⁴、X⁵、X⁶、X²⁰and X²¹Each of which is independently C or N;

Y¹and Y²Each of which is independently selected from the group consisting of: o, S, Se, CRR ', BR, SiRR' and NR;

one is a single bond and the other is a double bond;

G¹n or CR when in double bond, or O, NR or CRR' when in single bond;

G²n or CR when in double bond, or O, NR or CRR' when in single bond;

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

Any two substituents may be linked or fused together to form a ring.

8. The compound of claim 7, wherein R^AAnd R^BEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

9. The compound of claim 7, wherein R^AAnd R^BIs a substituted or unsubstituted group selected from the group consisting of: benzene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, pyrazole, triazole and N-heterocyclic carbenes.

10. The compound of claim 7, wherein X¹To X⁶Each independently is C.

11. The compound of claim 7, wherein two R' s^ATwo R^BTwo R^CAnd two R^DAt least one of the substituents is linked together to form a fused 6-membered carbocyclic or heterocyclic ring.

12. The compound of claim 7, wherein each Y is¹And Y²Independently selected from the group consisting of: o, S, CRR' and NR.

13. The compound of claim 1, wherein the ligand L_ASelected from the group consisting of:

wherein:

z is selected from the group consisting of: o, S, CRR ', BR, SiRR', and NR;

R¹and R²Each represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R¹and R²Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is

Any two substituents may be connected or fused to form a ring.

14. The compound of claim 13, wherein the ligand L_AIs selected from the group consisting of L_Aai-j、L_Abp-lAnd L_ACm-nWherein i is 1 to 19An integer, j is an integer from 1 to 126; p is an integer from 1 to 16, l is an integer from 1 to 189; m is an integer from 1 to 27, and n is an integer from 1 to 40; wherein for each i, L_Aai-jHas a structure defined as:

wherein for each j, R¹、R²、Y¹And Y²As defined in table 1 below:

wherein for each p, L_Abp-lHas a structure defined as:

wherein the pairAt each occurrence of l, R¹、R²And Y¹As defined in table 3 below:

wherein for each m, L_Acm-nHas a structure defined as:

wherein for each n, R¹And R²The definition is as follows:

15. the compound of claim 1, wherein the compound is of formula M (L)_A)_x(L_B)_y(L_C) Wherein L is_BAnd L_CEach is a bidentate ligand; and is

Wherein x is 1,2 or 3; y is 1 or 2; z is 0, 1 or 2; and x + y + z is the oxidation state of the metal M.

16. According to the rightThe compound of claim 15, wherein L_BAnd L_CEach independently selected from the group consisting of:

wherein:

each Y^1'、Y^2'And Y³To Y¹³Independently selected from the group consisting of carbon and nitrogen;

y' is selected from the group consisting of: BR (BR)_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_fAnd GeR_eR_f；

R_eAnd R_fMay be fused or linked to form a ring;

R_a、R_b、R_cand R_dEach independently represents zero substitution, mono substitution, or up to a maximum substitution for its associated ring;

R_a、R_b、R_c、R_d、R_eand R_fEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is

R_a、R_b、R_cAnd R_dAny two adjacent substituents of (a) may be fused or linked to form a ring or form a multidentate ligand.

17. The compound of claim 14, wherein the compound has the formula Ir (L)_A)₃Ir of the formula_A)(L_B)₂Or formula Ir (L)_A)₂(L_B) Wherein L is_AIs selected from the group consisting of L_Aai-j、L_Abp-lAnd L_Acm-nAnd L is a group of_BSelected from the group consisting of:

18. the compound of claim 1, wherein the compound has the structure of formula IIA:

wherein:

m is Pd or Pt;

ring E and ring F are each independently a 5-membered, 6-membered carbocyclic or heterocyclic ring;

x is C or N;

a single bond when X is N, or a double bond when X is C, and if

Is a double bond, the other two are single bonds;

Z³to Z⁶Each independently is C or N;

R^Eand R^FEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring;

L¹、L²and L³Each independently is a 1 atom linking group, a 2 atom linking group, or a direct bond;

m, n and p are each independently 0 or 1, wherein m + n + p is 2 or 3;

R^Eand R^FEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, and mixtures thereof,Nitriles, isonitriles, thio groups, and combinations thereof;

X²to X⁵Each independently is C or N;

Y¹and Y²Each of which is independently selected from the group consisting of: o, S, Se, CRR ', SiRR' and NR; and is

Any two substituents may be linked or fused together to form a ring.

19. An Organic Light Emitting Device (OLED), comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer contains a ligand L comprising formula I_AThe compound of (1):

wherein:

x is C or N;

Z¹and Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C;

ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring;

R^A、R^B、R^Cand R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R^A、R^B、R^Cand R^DEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinoAcyl, sulfonyl, phosphino, and combinations thereof; and is

Any two substituents may be connected or fused to form a ring,

wherein the ligand L_AComplexed to metal M via two indicated dotted lines;

wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and is

Wherein said ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

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

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer contains a ligand L comprising formula I_AThe compound of (1):

wherein:

x is C or N;

Z¹and Z²Each independently is C or N;

a single bond when X is N, or a double bond when X is C;

ring a, ring B, ring C, and ring D are each independently a 5-or 6-membered heterocyclic or carbocyclic ring;

R^A、R^B、R^Cand R^DEach represents zero, mono, or up to the maximum permissible substitution of its associated ring;

R^A、R^B、R^Cand R^DEach of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkylA group, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is

Any two substituents may be connected or fused to form a ring,

wherein the ligand L_AComplexed to metal M via two indicated dotted lines;

wherein the metal M is selected from the group consisting of: ru, Os, Ir, Pd, Pt, Cu, Ag, and Au, and can coordinate with other ligands; and is

Wherein said ligand L_AMay be linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

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