CN112341498A

CN112341498A - Organic electroluminescent material and device

Info

Publication number: CN112341498A
Application number: CN202010788139.2A
Authority: CN
Inventors: M·C·马克尼斯; 斯科特·比尔斯; 陈小凡; 格扎·西盖蒂; 约瑟夫·A·马克尔; 贾森·布鲁克斯
Original assignee: Universal Exhibition Co
Current assignee: Universal Exhibition Co; Universal Display Corp
Priority date: 2019-08-08
Filing date: 2020-08-07
Publication date: 2021-02-09

Abstract

The present invention relates to organic electroluminescent materials and devices. Providing a formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Description

Organic electroluminescent material and device

CROSS-REFERENCE TO RELATED APPLICATIONS

Priority of united states provisional application No. 62/884,329 filed 2019, 8, 119(e) is claimed in this application according to 35u.s.c. § 119(e), the entire contents of which are incorporated herein by reference.

Technical Field

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

Background

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

Iridium complexes with a fastening (strained) carbene ligand are provided. The iridium complex comprises an N-heterocyclic carbene (NHC) ligand which contains a group that binds the NHC to a cyclometallated benzene ring. When iridium complexes are used as emitter dopants in OLEDs, these ligands provide complexes that exhibit improved device lifetimes compared to comparative complexes where the NHC is not connected to a cyclometallated phenyl group.

In one aspect, the present disclosure provides a formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

Wherein: x¹To X⁹Each independently is C or N; r^A、R^BAnd R^CEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; y is a one-atom linker and Z is a two-atom linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t is¹And T²Is C; r, R ', R', R¹、R²、R^A、R^BAnd R^CEach independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is 1 or 2; y and z are each independently 0, 1 or 2; and x + y + z is 3; wherein if L is_AHaving the formula I, then L_BAnd L_CEach independently selected from the group consisting of:

wherein: y is¹To Y¹³Each independently selected from the group consisting ofGroup (2): c and N; 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 joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is selected from the group consisting of: B. al, Ga and In; l is_A、L_BAnd L_CAny of which can be joined together to form a tetradentate or hexadentate ligand; if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate monoanionic ligand; and two substituents may be joined or fused together to form a ring.

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

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

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

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 "siliconAlkyl "means-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, trimethyleneBenzene, 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, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, borinyl, 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, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, oxyboronyl, and combinations thereof.

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

In other cases, most 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 it represents a single substitution, thenA 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 optionally join or be 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

Formula I

Or formula II

wherein: y is¹To Y¹³Each independently selected from the group consisting of: c and N; 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 joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently of the others is hydrogen orA substituent selected from the group consisting of the general substituents defined herein; x is selected from the group consisting of: B. al, Ga and In; l is_A、L_BAnd L_CAny of which can be joined together to form a tetradentate or hexadentate ligand; if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate monoanionic ligand; and two substituents may be joined or fused together to form a ring.

In some embodiments, L_AHas the formula I, and L_BAnd L_CEach independently selected from the group consisting of:

wherein R is_a、R_b、R_c、R_d、R_e、R_fAnd R_gAs defined above.

In some embodiments, R, R ', R', R¹、R²、R^A、R^BAnd R^CEach independently is hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

In some embodiments, Y is selected from the group consisting of: o, NR ', CR ' R ", and SiR ' R".

In some embodiments, X¹To X⁶Each is C.

In some embodiments, R is aryl, heteroaryl, alkyl, or cycloalkyl.

In some embodiments, each R is^AIs H.

In some embodiments, each R is^BIs H.

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

and is

Wherein Z is selected from the group consisting of the structures in the following Z list:

in some embodiments of the compounds, the linking atoms in Z are each CR' R ". In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl and heteroaryl.

In some embodiments of the compounds, one of the two linking atoms in Z is SiR 'R "and the other is CR' R". In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl and heteroaryl.

In some embodiments of the compounds, one of the two linking atoms in Z is O or S, and the other is CR 'R "or SiR' R". In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl and heteroaryl.

In some embodiments of the compound, R¹Selected from the group consisting of: alkyl, cycloalkyl, aryl and heteroaryl.

In some embodiments, R²Selected from the group consisting of: hydrogen, alkyl, cycloalkyl, aryl and heteroaryl.

In some embodiments, X⁷、X⁸And X⁹Each is C.

In some embodiments, each R is^CIs H.

In some embodiments of compounds wherein Y is selected from the group consisting of the list of Y and Z is selected from the group consisting of the list of Z, ligand L_AHaving a structure according to formula I-1

And is selected from the group consisting of: based on numbering scheme L_A1-(y)(a)(i)(j)(k)(l)(m)，L_A1- (1) (3) (1) (1) (1) (1) (1) to L_A1- (37) (14) (14) (14) (14) (14) (14), or

Ligand L_AHaving a structure according to formula II-1

And is selected from the group consisting of: based on numbering scheme L_A2-(z)(a)(i)(j)(k)，L_A2- (1) (3) (1) (1) (1) to L_A2-(206)(14)(14)(14)(14)；

Wherein R is^AHaving R^AaStructure of (1), R^IHaving R^AiStructure of (1), R^JHaving R^AjStructure of (1), R^KHaving R^AkStructure of (1), R^LHaving R^AlStructure of (1), R^MHaving R^AmIs connected withStructuring;

in the formula I-1, Y has S^yIn formula II-1, Z has S'^zThe structure of (1);

y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, i, j, k, l and m are each independently an integer from 1 to 14; and is

R^A1To R^A14Has a structure defined as:

in some embodiments of the compounds, when L_AHaving the formula II, L_BAnd L_CMay each be independently selected from the group consisting of:

wherein: y is¹To Y¹³Each independently selected from the group consisting of: carbon and nitrogen; y' is selected from the group consisting of: BR (BR)_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_fAnd GeR_eR_f；R_eAnd R_fMay be fused or joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is 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 X is selected from the group consisting of: B. al, Ga and In; r_a、R_b、R_cAnd R_dTwo adjacent substituents in (a) may be fused or joined to form a ring or form a multidentate ligand.

in which L is_AIn some embodiments of the compounds having formula I-1 or formula II-1, the compound is selected from the group consisting of: ir [ (L)_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) And Ir [ (L)_A2-(z)(a)(i)(j)(k)](L_Bq)₂The structure of which is as defined above; wherein y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, i, j, k, l, and m are each independently an integer from 1 to 14; wherein q is an integer from 1 to 446; and wherein L_B1To L_B446Has the following structure:

in which L is_AIn some embodiments of the compounds having formula I-1 or formula II-1, the compound is selected from the group consisting of: ir [ (L)_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) And Ir [ (L)_A2-(z)(a)(i)(j)(k)](L_Bq)₂(ii) a Wherein y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, i, j, k, l, and m are each independently an integer from 1 to 14; wherein q is an integer selected from the group consisting of: 147. 148, 149, 150, 214, 216, 366, 375, 382, 397, 415, 422, 433 and 440. In some embodiments, q is an integer selected from the group consisting of: 214. 216, 366, 388, 391, 397, 415, 416, 418, 433, 434 and 440.

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

C. OLEDs and devices of the present disclosure

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

The OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

Wherein: x¹To X⁹Each independently is C or N; r^A、R^BAnd R^CEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; y is a one-atom linker and Z is a diradicalA sub-linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t is¹And T²Is C; r, R ', R', R¹、R²、R^A、R^BAnd R^CEach independently is 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; x is 1 or 2; y and z are each independently 0, 1 or 2; and x + y + z is 3; wherein if L is_AHaving the formula I, then L_BAnd L_CEach independently selected from the group consisting of:

wherein: y is¹To Y¹³Each independently selected from the group consisting of: c and N; 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 joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen radical,Alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, boroxy, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; x is selected from the group consisting of: B. al, Ga and In; l is_A、L_BAnd L_CAny of which can be joined together to form a tetradentate or hexadentate ligand; if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate monoanionic ligand; and two substituents may be joined or fused together to form a ring.

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 group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5, 9-dioxa-13 b-boranaphtho [3,2,1-de ] anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza- (5, 9-dioxa-13 b-boranaphtho [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 emission region may comprise the formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

Wherein: x¹To X⁹Each independently is C or N; r^A、R^BAnd R^CEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; y is a one-atom linker and Z is twoAn atomic linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t is¹And T²Is C; r, R ', R', R¹、R²、R^A、R^BAnd R^CEach independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is 1 or 2; y and z are each independently 0, 1 or 2; and x + y + z is 3; wherein if L is_AHaving the formula I, then L_BAnd L_CEach independently selected from the group consisting of:

wherein: y is¹To Y¹³Each independently selected from the group consisting of: c and N; 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 joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is selected from the group consisting of: B. al, Ga and In; l is_A、L_BAnd L_CAny of which can be joined together to form a tetradentate or hexadentate ligand; if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate and a single yinAn ionic ligand; and two substituents may be joined or fused together to form a ring.

In some embodiments of the emissive region, the compound may be an emissive dopant or a non-emissive dopant. In some embodiments, the emissive region further comprises a host, wherein the host contains at least one group selected from the group consisting of: metal complexes, triphenylenes, carbazoles, dibenzothiophenes, dibenzofurans, dibenzoselenophenes, aza-triphenylenes, aza-carbazoles, aza-dibenzothiophenes, aza-dibenzofurans, and aza-dibenzoselenophenes. In some embodiments, the subject is selected from the group consisting of the structures listed in the subject groups defined herein.

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 OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise the formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

wherein: y is¹To Y¹³Each independently selected from the group consisting of: c and N; 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 joined to form a ring; r_a、R_b、R_c、R_d、R_g、R_hAnd R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and R is_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is selected from the group consisting of: B. al, Ga and In; l is_A、L_BAnd L_CAny of which can be joined together to form a tetradentate or hexadentate ligand; if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate monoanionic ligand; and two substituents may be joined or fused together to form a ring.

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. Theory and use of barrier layersDescribed in 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, thiopheneBenzofuran, 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 another aspect, 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: by cyclization of aromatic hydrocarbonsCompound (la): 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.

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.

E. Experimental data

Ligand L_A2Synthesis of (9), (3), (1) and (1)

1-phenyl-1H-imidazole (5.0g, 34.7mmol, 1.0 equiv.) was dissolved in THF (200mL) and cooled to-78 deg.C for 45 min. Butyllithium (13.9mL, 34.7mmol, 1.0 eq) was added dropwise to the stirred mixture over 30 minutes and stirred at room temperature for 2 hours. Tert-butylchlorodimethylsilane (5.25g, 34.7mmol, 1.0 equiv.) was dissolved in THF (50mL) and added dropwise over 15 minutes. The reaction mixture was stirred at 23 ℃ for 2 hours. The reaction was concentrated under reduced vacuum and diluted with EtOAc (500mL) with saturated NaCl_(aq)(3X 300mL), water (3X 300mL), and Na₂SO₄And (5) drying. The mixture was concentrated under reduced pressure and purified on silica gel to give the product as a clear oil (8.0g, 31.0mmol, 90% yield).

2- (tert-butyldimethylsilyl) -1-phenyl-1H-imidazole (4.04g, 15.48mmol, 1.0 eq) was dissolved in DCM (160 mL). N-bromosuccinimide (2.62g, 17.7mmol, 0.95 equivalents) was added to the stirred mixture over 15 minutes, and the mixture was stirred at room temperature for 26 hours. The reaction mixture was loaded onto celite and purified on silica gel to give the pure product as a yellowish oil (4.20g, 80% yield).

5-bromo-2- (tert-butyldimethylsilyl) -1-phenyl-1H-imidazole (4.29g, 12.7mmol, 1.0 equiv.) was dissolved in THF (40mL) and the solution was cooled to-78 deg.C for 45 min. Isopropyl magnesium chloride (10.8mL, 14.0mmol, 1.1 eq) was added dropwise to the stirred mixture over 15 minutes and stirred at room temperature for 2 hours. The reaction was cooled to 0 ℃ and pivaloyl chloride (3.15mL, 25.4mmol, 2.0 equiv.) was added dropwise over 15 minutes. The reaction mixture was stirred at room temperature for 3 hours and then quenched with MeOH, diluted with EtOAc (200mL), saturated NaCl_(aq)(3X 150mL), DI water (3X 150mL), and Na₂SO₄And (5) drying. The mixture was concentrated under reduced pressure and purified on silica gel to give the product as a yellow glassy solid (2.2g, 12.7mmol, 51% yield).

1- (2- (tert-butyldimethylsilyl) -1-phenyl-1H-imidazol-5-yl) -2, 2-dimethylpropan-1-one (2.00g, 5.87mmol, 1 eq) was dissolved in THF (20mL) and the mixture was cooled to-78 ℃ for 30 min. To the solution was added methyllithium (4.40mL, 7.04mmol, 1.2 equiv) dropwise. The reaction was stirred at-78 ℃ for 3 hours and then saturated NH at 0 ℃₄Quenched with Cl and diluted with EtOAc (200mL) with saturated NH₄Cl (3X 100mL), saturated brine (3X 100mL) and water (3X 100 mL). Purification on silica gel afforded the product as a white solid (1.75g, 83% yield).

2- (2- (tert-butyldimethylsilyl) -1-phenyl-1H-imidazoleOxazol-5-yl) -3, 3-dimethylbut-2-ol (1.72g, 4.87mmol, 1 eq) was dissolved in DCM (100mL) and cooled to 0 ℃. Aluminum trichloride (3.20g, 23.9mmol 5 eq) was added in one portion. The reaction mixture turned dark red in color and was stirred at 0 ℃ for 1 hour, then warmed to 40 ℃ for 18 hours. The reaction mixture was cooled to 0 ℃ and quenched with NaOH (aq), diluted with EtOAc (300mL), washed with brine (3X 100mL) and water (3X 100mL), and over Na₂SO₄And (5) drying. After evaporation, the crude material was dissolved in THF (50mL) and 6N HCl (50mL) was added at room temperature. The mixture was stirred at room temperature for 6 hours, followed by complete removal of the TBS protecting group. Purification on silica gel (120g) gave the product as a white film (805mg, 75% yield).

4,4,5, 5-tetramethyl-4, 5-dihydroimidazo [1,5-a ] quinoline (3.7g, 16.4mmol, 1 eq.) and acetonitrile (50mL) are added to a dry sealed tube. Methyl iodide-d 3(1.3mL, 19.6mmol, 1.2 equiv.) was added to the stirred mixture. The tube was sealed and heated to 95 ℃ overnight. The solution was concentrated under reduced pressure to give a pale yellow solid. The solid was washed with ice cold diethyl ether (100mL) and dried in a vacuum oven to give pure product as a light yellow solid (5.3g, 14.3mmol, 88% yield).

Ligand L_ASynthesis of 1- (3) (3) (1) (1) (1) (1) (1)

A mixture of 2- (2-aminophenyl) propan-2-ol (2.28g, 15.1mmol), 1-iodo-2-nitrobenzene (3.75g, 15.1mmol), S-Phos (0.495g, 1.21mmol), Pd2(dba)3(0.276g, 0.302mmol) and cesium carbonate (7.37g, 22.6mmol) in 120mL toluene was refluxed for 20 hours. After filtration through celite and removal of the solvent, the crude material was purified by column chromatography to give 3.9g of the product as an orange solid (95%).

2- (2- ((2-nitrophenyl) amino) phenyl) propan-2-ol (2g, 7.34mmol) was stirred in 50mL of polyphosphoric acid and 2mL of acetic acid at 50 ℃ for 12 hours. The reaction was poured into ice water and the red solid was filtered, washed with water and dried to give 1.8g of product, 96% yield.

9, 9-dimethyl-4-nitro-9, 10-dihydroacridine (16g, 62.9mmol) was hydrogenated in two 8g batches by stirring a solution of the starting material in EtOAc over 10% Pd/C under 50psi of hydrogen. Filtration through celite and removal of the solvent gave 12.2g of product (86%).

A mixture of 9, 9-dimethyl-9, 10-dihydroacridin-4-amine (12g, 53.5mmol), triethoxymethane (7.93g, 53.5mmol) and p-toluenesulfonic acid monohydrate (1.02g, 5.25mmol) was stirred at 80 ℃ for 16 hours. After combining with another 1g batch, the mixture was diluted with ethyl acetate and washed with aqueous Na2HCO3 solution. After drying and removal of the solvent under reduced pressure, the crude mixture was purified by column chromatography to give 11.14g of the product as a brown oil.

A mixture of 6, 6-dimethyl-6H-imidazo [4,5,1-de ] acridine (2.76g, 11.8mmol) and iodomethane (10g, 71mmol) in 100mL of MeCN was stirred for 3 days. The resulting solid was filtered and washed with ether to give 3.5g of the product as a white solid (79%).

Ligand L_ASynthesis of 1- (4) (3) (1) (1) (1) (1) (1)

2-bromoaniline (40g, 233mmol) was added portionwise to a suspension of sodium hydride (18.60g, 465mmol) in THF (400mL) at room temperature. After 2h, 1-bromo-2-fluoro-3-nitrobenzene (51.2g, 233mmol) in THF (200mL) was added at 0 ℃. The mixture was stirred at room temperature for 2 hours. The mixture was poured into ice water and extracted with DCM. The organic layer was washed with 2N HCl, dried, and the solvent was removed in vacuo. The resulting dark red oil was wet-milled with heptane to give a yellow solid, 68g (79%).

2-bromo-N- (2-bromophenyl) -6-nitroaniline (70g, 188mmol), iron (105g, 1882mmol) and NH₄Cl (101g, 1882mmol) inⁱThe mixture of PrOH (500 ml)/formic acid (505ml, 1.32E +04mmol) was heated at 80 ℃ for 12 hours. After cooling to room temperature, the mixture was usedⁱPrOH was diluted, filtered, and the solvent was removed under reduced pressure. The residue was neutralized with aqueous NaOH and extracted with DCM. The organic phase was evaporated to give 60g of product (91%).

Butyllithium (47.7ml, 119mmol) was added to a solution of 7-bromo-1- (2-bromophenyl) -1H-benzo [ d ] imidazole (20g, 56.8mmol) at-10 ℃. The mixture was stirred at-10 ℃ to 0 ℃ for 1 hour and then cooled to-78 ℃. Dichlorodimethylsilane (8.07g, 62.5mmol) was added dropwise and the solution was allowed to warm slowly to room temperature. The reaction was quenched with water, diluted with EtOAc, and the solvent was removed under reduced pressure. The crude mixture was purified by column chromatography to give the product as an orange oil, 10.9g (77%).

6, 6-dimethyl-6H-2, 10 b-diaza-6-silaxanthene (1.31g, 5.23mmol) and iodomethane (1.95mL, 31.4mmol) were stirred at room temperature in 40mL MeCN for 16H. An additional 1mL of methyl iodide was added and the mixture was stirred for an additional 5 hours. The solvent was removed in vacuo and the residue wet-milled with ether to give the product as a white solid, 1.70g (83%).

Ligand L_ASynthesis of 2- (109) (3) (1) (1) (1)

A solution of 2-TBS-phenylimidazole in dry THF (80mL) was cooled to-78 deg.C and n-BuLi (6mL, 2.5M in hexanes) was added dropwise. The mixture was stirred at low temperature for 30 minutes. A solution of bromodimethyl (prop-1-en-2-yl) silane (3.98g) (US20190051845A 12019-02-14) in THF (10mL) was added dropwise at the same temperature and allowed to stir for an additional 30 minutes. The reaction was allowed to slowly warm to room temperature and stirred for an additional 1 hour. The reaction was quenched with cold water (10mL) and brine (20mL) and extracted into ethyl acetate. The organics were concentrated and purified by column chromatography to give the product as a white solid (2.5g, 47%) which was purified by adding 0.1 equivalent of TsOH (H) to the crude product₂O) is refluxed to remove the protecting group.

5- (diisopropyl (prop-1-en-2-yl) silyl) -1-phenyl-1H-imidazole (1g, 4.13mmol) and Eton's reagent (14mL) were stirred at room temperature for 16H. The reaction mixture was slowly poured onto cold sodium bicarbonate solution (150mL) and extracted into EtOAc. The organic layer was concentrated and purified by column chromatography to give 760mg of product (76%).

A solution of 4,4,5, 5-tetramethyl-4, 5-dihydrobenzo [ e ] imidazo [1,5-a ] [1,3] azasilane (520mg, 2.14mmol) and iodomethane (0.46g, 3.22mmol) in acetonitrile (6mL) was heated in a sealed tube at 80 ℃ for 16 h. The solvent was removed in vacuo and the residue wet-milled in ether (60mL) to give the product as a white solid (788mg, 96% yield).

Ligand L_ASynthesis of 2- (111) (3) (1) (1) (1)

A solution of 2-TBS-phenylimidazole in dry THF (100mL) was cooled to-78 deg.C and n-BuLi (6.2mL, 2.5M in hexanes) was added dropwise. The mixture was stirred at low temperature for 30 minutes. A solution of bromodiisopropyl (prop-1-en-2-yl) silane (5.23g, 1.5 eq) (US20190051845a 12019-02-14) in THF (25mL) was added dropwise at the same temperature and allowed to stir for an additional 30 minutes. The reaction was allowed to slowly warm to room temperature and stirred for an additional 1 hour. The reaction was quenched with methanol (10mL) and concentrated at room temperature under reduced pressure. Flash purification by column chromatography gave the product as a white solid (5.15g, 84% yield) which was purified by passing it through a column containing 0.1 equivalent of TsOH (H)₂O) refluxing the toluene solution to quantitatively remove the protecting group.

5- (diisopropyl (prop-1-en-2-yl) silyl) -1-phenyl-1H-imidazole (2.5g, 8.38mmol) and Eton's reagent (28mL) were stirred at room temperature for 16H. The reaction mixture was slowly poured onto cold sodium bicarbonate solution (250mL) and extracted into EtOAc. The organic layer was concentrated and purified by column chromatography to give 1.9g of product (76%).

A solution of 4, 4-diisopropyl-5, 5-dimethyl-4, 5-dihydrobenzo [ e ] imidazo [1,5-a ] [1,3] azasilane (1.8g, 6.03mmol) and iodomethane (1.3g, 9.05mmol) in acetonitrile (15mL) was heated in a sealed tube at 80 ℃ for 16 hours. The solvent was removed in vacuo and the residue wet-milled in ether (60mL) to give the product as a white solid (2.35g, 88% yield).

General procedure for the preparation of the Compounds of the invention

The method A comprises the following steps:

(a) the method comprises the following steps 2-iodine-4, 4,5, 5-tetramethyl-2- (methyl-d 3) -1,2,4, 5-tetrahydro imidazo [1,5-a ]]Quinolin-2-ium-1-salt (1.335g, 3.59mmol) and silver oxide (0.416g, 1.797mmol) were suspended in dichloromethane (60ml) containing 4A molecular sieves (1.5 g). The mixture was stirred at room temperature for 1.5 hours, at which time [ Ir (COD) Cl was added]₂(1.2g,1.797 mmol). After stirring for one hour, the suspension was filtered through celite, and the filter pad was washed with DCM (3 × 25 mL). The solvent was removed from the filtrate under reduced pressure to give an ir (cod) cl (nhc) adduct (2.0g, 96%) as a yellow solid. (b) The method comprises the following steps Ir (COD) Cl (NHC) complex (3.46mmol) and 4, 4-dimethyl-3, 3, 7-tris (methyl-d 3) -2-phenyl-3, 4-dihydrodibenzo [ b, ij)]Imidazole [2,1,5-de]Quinolizine (2.77g, 6.93mmol) was stirred together in triethyl phosphate (20mL) in a 100mL round bottom flask and the mixture was bubbled with nitrogen for 15 minutes. The mixture was heated to 150 ℃ for 16 hours. Once cooled to room temperature, the mixture was purified by column chromatography to give two hybrid planar complexes as a light yellow solid.

The method B comprises the following steps:

(a) the method comprises the following steps A250 mL round-bottomed flask was charged with 4- (methyl-d 3) -2, 5-diphenylpyridine (5.0g, 20.13mmol) and IrCl₃(H₂O)₃(2.367g，6.71mmol) in 120mL of 3: 12-ethoxyethanol water under reflux was stirred for 16 h. After cooling to room temperature, the yellow suspension was filtered and the solid was washed with MeOH and water to give [ L as a yellow solid₂IrCl]₂4.06 g. Will [ L ]₂IrCl]₂(4.0g, 2.77mmol) was stirred in DCM (40 mL). Silver triflate (1.49 g, 5.81mmol) was dissolved in methanol (20mL) and added to the DCM solution, and the heterogeneous mixture was stirred at room temperature for 16 h. Filtration through celite and removal of solvent from the filtrate gave 4.5g [ L₂Ir(MeOH)₂]OTf. (b) The method comprises the following steps Bubbling into nitrogen [ L₂Ir(MeOH)₂]To a suspension of OTf (2.4g, 3.7mmol) in 1, 2-dichlorobenzene (25mL) was added 4,4,5, 5-tetramethyl-2- (methyl-d 3) -4, 5-dihydroimidazo [1,5-a ]]Quinolin-2-ium-3-ium salt (0.9g, 3.7mmol) and nitrogen was again bubbled for 5 minutes. Potassium tert-butoxide (0.6g, 7.4mmol) was added and the reaction was heated at 80 ℃ for 36 h. The reaction mixture was cooled to room temperature and coated directly onto celite. Column chromatography was performed to give the desired compound, which was dissolved in THF and photoisomerized by irradiation at 350 nm. Progress was monitored by HPLC and after 1 week the reaction mixture was purified by column chromatography to give the desired compound of formula (xxvi) as a yellow solid.

Photoluminescent properties of the compounds of the invention:

TABLE 1 characterization of examples of Compounds of the invention

The structures of the compounds of the invention listed in table 1 are as follows:

device experiment:

the OLEDs were grown on glass substrates pre-coated with an Indium Tin Oxide (ITO) layer having a sheet resistance of 15- Ω/sq. In any organic layerPrior to deposition or coating, the substrate was degreased with a solvent and then treated with oxygen plasma at 50W for 1.5 minutes at 100 mtorr and with UV ozone for 5 minutes. By thermal evaporation under high vacuum (<10-6 torr). The anode electrode is

Indium Tin Oxide (ITO). After manufacture, in a nitrogen glove box (<1ppm of H₂O and O₂) All devices were immediately encapsulated with an epoxy-sealed glass lid, incorporating the moisture absorber inside the package.

Example OLEDs were fabricated to incorporate the inventive emitter compound Ir [ L ]_A2-(9)(4)(1)(1)(1)]₂[L_B391]The device performance of (a) was compared with that of comparative compound 1. The devices in table 2 have, starting from the ITO surface, organic layers consisting in the following order:

a thick compound of 1(HIL),

A layer of Compound 2(HTL),

Compound 3(EBL),

Compound 4(EML) doped with 15% emitter,

A compound 5(BL),

Compound 6(ETL),

Compound 7(EIL), followed by

Al (cathode). The doping percentages are by volume. LE is the luminous efficiency in cd/A, and PE is the power efficiency in lm/W.

Table 2:

as can be seen from the device results presented herein, it was unexpectedly found that the efficiency of the compounds containing the element Z of the present invention was much higher compared to compounds not containing the element Z of the present invention. Each efficiency parameter had more than a 10% improvement, which was considered a significant improvement.

Claims

1. Formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

Wherein:

X¹to X⁹Each independently is C or N;

R^A、R^Band R^CEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring;

y is a one-atom linker and Z is a two-atom linker;

the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R ';

T¹and T²Is C;

R、R'、R"、R¹、R²、R^A、R^Band R^CEach independently is 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;

x is 1 or 2;

y and z are each independently 0, 1 or 2; and is

x+y+z＝3；

Wherein if L is_AHaving the formula I, then L_BAnd L_CEach independently selected from the group consisting of:

wherein:

Y¹to Y¹³Each independently selected from the group consisting of: c and N;

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_fCan be fused or joined to form a ring;

R_a、R_b、R_c、R_d、R_g、R_hand R_iEach independently represents zero substitution, mono substitution, or up to the maximum permissible substitution for its associated ring; and is

R_a、R_b、R_c、R_d、R_e、R_f、R_g、R_hAnd R_iEach independently is 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;

x is selected from the group consisting of: B. al, Ga and In;

L_A、L_Band L_CAny of which can be joined together to form a tetradentate or hexadentate ligand;

if L is_AHaving the formula II, then L_BAnd L_CEach is a bidentate monoanionic ligand; and is

Two substituents can be joined or fused together to form a ring.

2. The compound of claim 1, wherein L_AHas the formula I, and L_BAnd L_CEach independently selected from the group consisting of:

3. the compound of claim 1, wherein R, R', R ", R¹、R²、R^A、R^BAnd R^CEach independently is hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroarylNitriles, isonitriles, thio groups and combinations thereof.

4. The compound of claim 1, wherein Y is independently selected from the group consisting of: o, NR ', CR ' R ", and SiR ' R".

5. The compound of claim 1, wherein X¹To X⁶Each is C.

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

and is

Wherein Z is selected from the group consisting of:

7. the compound of claim 1, wherein the linking atoms in Z are each CR' R ".

8. The compound of claim 1, wherein one of the two linking atoms in Z is SiR 'R "and the other is CR' R".

9. The compound of claim 1, wherein one of the two linking atoms in Z is O or S, and the other is CR 'R "or SiR' R".

10. The compound of claim 6, wherein ligand L_AHaving a structure according to formula I-1

And is selected from the group consisting of: based on numbering scheme L_A1-(y)(a)(i)(j)(k)(l)(m)，L_A1- (1) (3) (1) (1) (1) (1) (1) to L_A1-(37)(14)(14)(14)(14)(14)(14)，

Or L_AHaving a structure according to formula II-1

Wherein:

wherein R is^AHaving R^AaStructure of (1), R^IHaving R^AiStructure of (1), R^JHaving R^AjStructure of (1), R^KHaving R^AkStructure of (1), R^LHaving R^AlStructure of (1), R^MHaving R^AmThe structure of (1);

in the formula I-1, Y has S^yIn formula II-1, Z has S'^zThe structure of (1);

R^A1To R^A14Has a structure defined as:

11. the compound of claim 1, wherein when L_AHaving the formula II, L_BAnd L_CEach independently selected from the group consisting of:

wherein:

Y¹to Y¹³Each independently selected from the group consisting of: carbon and nitrogen;

R_eAnd R_fCan be fused or joined to form a ring;

R_a、R_b、R_c、R_d、R_g、R_hand R_iEach 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_e、R_f、R_g、R_hand R_iEach independently is 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

X is selected from the group consisting of: B. al, Ga and In;

R_a、R_b、R_cand R_dTwo adjacent substituents in (a) can be fused or joined to form a ring or form a multidentate ligand.

12. The compound of claim 1, wherein when L_AHaving the formula II, L_BAnd L_CEach independently selected from the group consisting of:

13. the compound of claim 10, wherein the compound is selected from the group consisting of: ir [ (L)_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) And Ir [ (L)_A2-(z)(a)(i)(j)(k)](L_Bq)₂(ii) a Wherein q is an integer from 1 to 446; and wherein L_B1To L_B446Has the following structure:

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

15. an Organic Light Emitting Device (OLED), comprising: an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the formula Ir (L)_A)_x(L_B)_y(L_C)_zA compound wherein L_AHas the advantages of

Formula I

Or formula II

Wherein:

X¹to X⁹Each independently is C or N;

y is a one-atom linker and Z is a two-atom linker;

T¹and T²Is C;

x is 1 or 2;

y and z are each independently 0, 1 or 2; and is

x+y+z＝3；

wherein:

Y¹to Y¹³Each independently selected from the group consisting of: c and N;

R_eAnd R_fCan be fused or joined to form a ring;

x is selected from the group consisting of: B. al, Ga and In;

Two substituents can be joined or fused together to form a ring.

16. The OLED according to claim 15, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

17. The OLED of claim 16 wherein the host is selected from the group consisting of:

and combinations thereof.

18. The OLED according to claim 15 wherein the compound is a sensitizer and the OLED further comprises an acceptor; and wherein the receptor is selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

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

an anode;

a cathode; and

Formula I