Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Organometallic compounds are provided. Formulations comprising these organometallic compounds are also provided. Also provided are OLEDs and related consumer products that utilize these organometallic compounds.

Description

[0001] This application is a divisional application of the Chinese invention patent application with application number 202011448153.4, invention name organic electroluminescent materials and devices, and application date December 9, 2020.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 62 / 945,273, filed on December 9, 2019, the entire contents of which are incorporated herein by reference. Technical Field

[0004] 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 Art

[0005] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many materials used to make the devices are relatively inexpensive, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can make them more suitable for specific applications, such as manufacturing on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0006] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for use in applications such as flat panel displays, lighting, and backlighting.

[0007] One application of phosphorescent emitting molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, an absorption filter is used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. Summary of the invention

[0008] In one aspect, the present disclosure provides a ligand L comprising formula I A Compounds:

[0009]

[0010] Where Z 1 and Z 2 One of them is C and the other is N; K 1 and K 2 Each of the R is independently a direct bond, S or O; Ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; R A represents zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring; X 1 -X 7 Each of is independently N or CR; R and R A At least one of has the following structure:

[0011]

[0012] Where: X 8 -X 15 Each of which is independently N or CR', is bound to X of Formula I 1 -X 7 One of the rings A or X 8 -X 15 A specific one of them is C; the maximum number of N atoms that can be connected to each other in the ring is two; the remaining R and R A Each of R' and R is independently hydrogen, a substituent of Formula II, Formula III, or a substituent selected from the group consisting of general substituents defined herein; B Each of the ligands L is independently hydrogen, or a substituent selected from the group consisting of general substituents defined herein; A The metal M is coordinated by the indicated dashed line; the ligand L A can be linked to other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt and can coordinate with additional ligands; and any two adjacent R, R' or R A May be linked or fused together to form a ring.

[0013] In another aspect, the present disclosure provides a ligand L comprising Formula I as described herein A formulation of a compound of the invention.

[0014] In another aspect, the present disclosure provides an OLED having an organic layer containing a ligand L comprising Formula I as described herein. A of compounds.

[0015] In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer containing a ligand L comprising Formula I as described herein. A of compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 An organic light emitting device is shown.

[0017] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated. DETAILED DESCRIPTION

[0018] A. Terminology

[0019] Unless otherwise specified, the following terms used herein are defined as follows:

[0020] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" may actually be quite large. In some cases, a small molecule may include a repeating unit. For example, the use of a long chain alkyl group as a substituent does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example as a side group on a polymer backbone or as part of a backbone. Small molecules can also serve as the core portion of a dendritic polymer, which consists of a series of chemical shells built on the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small molecule emitter. A dendritic polymer can be a "small molecule", and all dendritic polymers currently used in the field of OLEDs are considered to be small molecules.

[0021] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed "above" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, there may be other layers between the first and second layers. For example, a cathode may be described as being "disposed "above" an anode even though various organic layers are present between the cathode and the anode.

[0022] 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.

[0023] When a ligand is believed to directly contribute to the photosensitive property of an emissive material, the ligand may be referred to as "photosensitive." When a ligand is believed not to contribute to the photosensitive property of an emissive material, the ligand may be referred to as "ancillary," but the ancillary ligand may alter the properties of the photosensitive ligand.

[0024] As used herein, and as will be generally understood by one skilled in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram with the vacuum energy level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0025] As used herein, and as one skilled in the art would generally understand, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are typically measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows different rules than work functions.

[0026] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0027] The term "acyl" refers to a substituted carbonyl (C(O)-R s ).

[0028] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0029] The term "ether" refers to -OR s Group.

[0030] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0031] The term "sulfinyl" refers to -S(O)-R s Group.

[0032] The term "sulfonyl" refers to -SO2-R s Group.

[0033] The term "phosphino" refers to -P(R s )3 groups, wherein each R s Can be the same or different.

[0034] The term "silyl" refers to -Si(R s )3 groups, wherein each R s Can be the same or different.

[0035] The term "boryl" refers to -B(R s )2 group or its Lewis adduct -B(R s )3 groups, wherein R s Can be the same or different.

[0036] In each of the above, R s It may be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0037] The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. In addition, the alkyl group may be optionally substituted.

[0038] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 3 to 12 ring carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. In addition, the cycloalkyl group may be optionally substituted.

[0039] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by 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, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0040] The term "alkenyl" refers to and includes straight and branched alkenyl groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced by 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 two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl or heteroalkenyl groups may be optionally substituted.

[0041] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are alkynyl groups containing two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.

[0042] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.

[0043] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. Aromatic heterocyclic groups can be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines, such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, heterocyclic groups can be optionally substituted.

[0044] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

[0045] 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 rings with 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof.

[0046] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine and benzimidazole and their respective corresponding aza analogs are of particular interest.

[0047] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl and heteroaryl are independently unsubstituted or substituted with one or more typical substituents.

[0048] In many cases, the general substituent is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0049] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, boryl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0050] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, boryl, aryl, heteroaryl, thio, and combinations thereof.

[0051] In other cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0052] The terms "substituted" and "substituted" refer to the bonding of substituents other than H to the relevant positions, such as carbon or nitrogen. For example, when R 1 When it represents a single substitution, one R 1 must not be H (i.e., substituted). Similarly, when R 1 When it indicates disubstituted, the two R 1 must not be H. Similarly, when R 1 When it indicates zero or no substitution, R 1 For example, it can be hydrogen with available valences for the ring atoms, such as the carbon atoms of benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atoms.

[0053] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents; and halogen, alkyl and aryl can be combined to form haloaralkyl. In one example, the term substitution includes a combination of two to four listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0054] The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH 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.

[0055] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be easily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951 and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entirety) respectively describe the deuteration of methylene hydrogen in benzylamine and the effective way to replace aromatic ring hydrogen with deuterium.

[0056] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another part, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0057] In some cases, a pair of adjacent substituents can be optionally joined or fused to form a ring. Preferred rings are five, six or seven-membered carbocyclic or heterocyclic rings, including two cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be immediately adjacent to each other on the same ring, or on two adjacent rings with two closest available substitutable positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene), as long as they can form a stable fused ring system.

[0058] B. Compounds of the Disclosure

[0059] In one aspect, the present disclosure provides a ligand L comprising formula I A Compounds:

[0060]

[0061] in:

[0062] Z 1 and Z 2 One of them is C and the other is N;

[0063] K 1 and K 2 Each of is independently a direct bond, S or O;

[0064] Ring A is a 5-membered or 6-membered carbocyclic ring or heterocyclic ring;

[0065] R A indicates zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring;

[0066] X 1 -X 7 Each of is independently N or CR;

[0067] R and R A At least one of has the following structure:

[0068]

[0069] Wherein: each wavy line represents a bond with the relevant part of Formula I;

[0070] X 8 -X 15 Each of which is independently N or CR', is bound to X of Formula I 1 -X 7 One of the rings A or X 8 -X 15 A specific one of them is C;

[0071] The maximum number of N atoms that can be connected to each other within the ring is two;

[0072] The remaining R and R A Each of is independently hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of general substituents defined herein;

[0073] R' and R B Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein;

[0074] Ligand L A Coordination to metal M is indicated by dashed lines;

[0075] Ligand L A Can be linked to other ligands to form tridentate or tetradentate ligands;

[0076] M is Pd or Pt and may be coordinated with additional ligands; and

[0077] Any two adjacent R, R' or R A May be joined or fused together to form a ring.

[0078] In some embodiments, one R may have a structure of Formula II or Formula III. A It may have a structure of Formula II or Formula III.

[0079] In some embodiments, in addition to R and R having a structure of Formula II or Formula III A Except for at least one of the A Each of which may independently be hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0080] In some embodiments, K 1 and K 2 Can each be a direct key. In some embodiments, K 1 or K 2 One of the can be O.

[0081] In some embodiments, X 1 -X 7 can be CR independently, and X 8 -X 15 Can be independently C or CR'. In some embodiments, X 1 -X 15 One of them can be N, and the rest for X 1 -X 7can be CR independently, and for X 8 -X 15 In some embodiments, X 1 -X 4 One of can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 5 -X 7 One of can be N, and X 1 -X 15 The rest of X 1 -X 7 can be CR independently, and for X 8 -X 15 In some embodiments, X 8 -X 11 One of can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 12 -X 15 One of can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 1 -X 15 Two of them can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 1 -X 7 Two of them can be N, and X 1 -X 15 The rest of X1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 8 -X 15 Two of them can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 In some embodiments, X 1 -X 7 One of them can be N, X 8 -X 15 One of can be N, and X 1 -X 15 The rest of X 1 -X 7 For X, they can be CR independently, and for X 8 -X 15 They can each independently be C or CR'.

[0082] In some embodiments, Z 1 Can be N, and Z 2 Can be C. In some embodiments, Z 1 Can be C, and Z 2 Can be N.

[0083] In some embodiments, ring A may be a 5-membered or 6-membered aromatic ring. In some embodiments, ring A may be selected from the group consisting of pyrimidine, pyridine, pyridazine, pyrazine, triazine, benzene, imidazole, triazole, pyrazole, isothiazole, oxazole and thiazole. In some embodiments, ring A may be selected from the group consisting of pyridine, pyrimidine, benzene and imidazole.

[0084] In some embodiments, the compound may comprise a ligand L of A :

[0085]

[0086] Where X 1 -X 15 , Z 1 , Z 2 , R, R A , R B and Ring A are all the same as defined above for Formula I.

[0087] In the above embodiments, ring A can be pyrimidine, pyridine, pyridazine, pyrazine, triazine, benzene, imidazole, triazole, pyrazole, isothiazole, oxazole or thiazole. In some embodiments, ring A can be pyridine, pyrimidine, imidazole or benzene.

[0088] In the above embodiments, R A It can be an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group or a combination thereof. A It can be an alkyl group or a cycloalkyl group.

[0089] In some embodiments, the ligand L A It may be a tetradentate ligand.

[0090] In some embodiments, the compound may have the structure of Formula VI:

[0091] in:

[0092] X 1 -X 6 Each of is independently N or CR;

[0093] R and R A At least one of has the following structure:

[0094]

[0095] Wherein: each wavy line represents a bond with the relevant part of Formula VI;

[0096] X 8 -X 15 Each of which is independently N or CR', is bound to X of Formula I 1 -X 6 One of the rings A or X 8 -X 15 A specific one of them is C; Ring C and D are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0097] K 1 , K 2 , K 3 or K 4 Each of is independently a direct bond, S or O, at least two of which are direct bonds;

[0098] Z 3 , Z 4 , Z 5 and Z 6 Each independently is C or N;

[0099] L, L 1 and L 2Each is independently selected from the group consisting of: direct bond, absence, O, S, CR"R"', SiR"R"', BR" and NR", wherein L 1 and L 2 At least one of them exists;

[0100] R C and R D Each represents zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring;

[0101] R", R"', R C and R D each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof;

[0102] M is Pd or Pt;

[0103] Any two adjacent R, R', R", R"', R A , R B , R C or R D may be linked or fused together to form a ring where chemically feasible; and X 1 -X 6 , X 8 -X 15 , Z 1 , Z 2 , R A , R B and Ring A are all the same as defined above.

[0104] In some of the above embodiments, ring C may be a 5-membered or 6-membered heteroaromatic ring. In some embodiments, ring C and ring D may both be 6-membered aromatic rings. In some embodiments, ring C and ring D may both independently be pyrimidine, pyridine, pyridazine, pyrazine, triazine or benzene. In some embodiments, ring D may be a 5-membered heteroaromatic ring. In some embodiments, ring D may be an imidazole, triazole, pyrazole, isothiazole, oxazole or thiazole ring.

[0105] In some of the above embodiments, the two R D Substituents may be linked to form a fused ring. C The substituents may be linked to form a fused ring system. In some embodiments, the fused ring may be a 6-membered aromatic ring.

[0106] In some embodiments, K 1 , K 2 , K 3 or K 4Each of K can be independently a direct key. In some embodiments, K 1 , K 2 , K 3 or K 4 One of may be O. In some embodiments, K 1 or K 2 One of may be O. In some embodiments, K 3 or K 4 One of the can be O.

[0107] In some of the above embodiments, Z 3 Can be N and Z 6 Can be C. In some embodiments, Z 3 Can be C and Z 6 Can be N. In some embodiments, Z 3 and Z 6 All can be C. In some embodiments, Z 4 and Z 5 Can be C. In some embodiments, Z 4 Can be N and Z 5 Can be C.

[0108] In some of the above embodiments, L may be a direct bond. In some embodiments, L may be NR". In some embodiments, L 1 In some embodiments, L 2 It can be O, NR" or CR"R"'. In some embodiments, L 2 In some embodiments, L may be a direct bond, L 1 may not exist, and L 2 Can be O.

[0109] In some embodiments, M may be Pd. In some embodiments, M may be Pt.

[0110] In some embodiments, the compound may be selected from the group consisting of:

[0111]

[0112] Where: X 1 -X 6 Each of is independently N or CR; and at least one R or R A Has the following structure:

[0113]

[0114] Where: Each wavy line represents a bond to the relevant portion of the base compound structure;

[0115] X 8-X 15 Each of which is independently N or CR', bonded to X 1 -X 6 One of the X 8 -X 15 A specific one of them is C;

[0116] R X and R Y are each independently selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

[0117] R E is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and

[0118] X 1 -X 6 , X 8 -X 15 , Z 1 , Z 2 , R A , R B , R C , R D , L 1 and L 2 All are the same as defined above for Formula I and Formula VI.

[0119] In the above embodiments, L 1 In the above embodiment, L 2 Can be O, NR" or CR"R"'.

[0120] In some embodiments, the compound can be selected from the group consisting of the structures listed in Table 1 below:

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] In some embodiments, the compound can be selected from the group consisting of: compound (I)-I-(A'i)(Bj)(Bk) to compound (I)-XIV-(A'i)(Bj)(Bk), wherein l, i, j and k are as defined below, and each compound has the formula Pt(L A )(L B ), the formula has the following structure:

[0127]

[0128] Where L A Having the structure shown above and selected from the group consisting of: I-(A'i)(Bj)(Bk) to XIV-(A'i)(Bj)(Bk), wherein i is an integer from 1 to 7 and k is an integer from 1 to 47, and when i=1 to 3, j is an integer from 1 to 41, and when i=4 to 7, j is an integer from 1 to 47;

[0129] Where L B Having the structure shown above and selected from the group consisting of L1, wherein l is an integer from 1 to 230107;

[0130] wherein Ring C and D are as defined above for Formula VI; or

[0131] The compound may be selected from the group consisting of compounds [I-(A'i)(Bj)(Bk)][I-(A'm)(Bn)(Bo)] to compounds [XIV-(A'i)(Bj)(Bk)][XIV-(A'm)(Bn)(Bo)], each having the formula Pt(L A )(L C ), the formula has the following structure:

[0132] Where L A As defined above;

[0133] Where L C having the structure shown above and selected from the group consisting of: I-(A'm)(Bn)(Bo) to XIV-(A'm)(Bn)(Bo);

[0134] wherein L1 at each occurrence independently has the structure defined in List 2 below, wherein each wavy line in each structure is independently used to connect to L A The relevant part:

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] Where A1 to A30 have the following structure:

[0160]

[0161] And wherein R1 to R330 have the following structure:

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179] Where L A and L C Independently has the structure defined in Listing 3 below:

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186] Where A'1 to A'7 have the following structure:

[0187]

[0188] Among them, B1 to B47 have the following structures:

[0189]

[0190]

[0191] In some embodiments, each of Bj and Bk can be independently selected from the group consisting of: B1, B2, B3, B9, B10, B16, B18, B20, B22, B24, B25, B27, B29, B31, B32, B33, B34, B34, B40, B44, B45 and B46.

[0192] In some embodiments, Ai at each occurrence may be independently selected from the group consisting of: A1, A2, A3, A7, A10, A11, A12, A13, A19, A20, A21, A23, and A29.

[0193] In some embodiments, R 1 R106, R130, R134, R135, R136, R137, R316, R317, R321, R322, R328, R329, and R330.

[0194] In some embodiments, the compound can be selected from the group consisting of the following List 4:

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] C. OLEDs and Devices of the Present Disclosure

[0204] In another aspect, the present disclosure also provides an OLED device comprising an organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0205] In some embodiments, the organic layer may contain a ligand L comprising Formula I A Compounds:

[0206]

[0207] Where Z 1 and Z 2 One of them is C and the other is N; K 1 and K 2 Each of the R is independently a direct bond, S or O; Ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; R A represents zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring; X 1 -X 7 Each of is independently N or CR; R and R A At least one of has the following structure:

[0208]

[0209] Where: X 8 -X 15 Each of which is independently N or CR', is bound to X of Formula I 1 -X 7 One of the rings A or X 8 -X 15 A specific one of them is C; the maximum number of N atoms that can be connected to each other in the ring is two; the remaining R and R A Each of R' and R is independently hydrogen, a substituent of Formula II, Formula III, or a substituent selected from the group consisting of general substituents defined herein; B Each of the ligands L is independently hydrogen, or a substituent selected from the group consisting of general substituents defined herein; A The metal M is coordinated by the indicated dashed line; the ligand L A can be linked to other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt and can coordinate with additional ligands; and any two adjacent R, R' or R A May be joined or fused together to form a ring.

[0210] 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.

[0211] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a benzo-fused thiophene or a benzo-fused furan containing triphenylene, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 、OAr1、N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar1、Ar1-Ar2、C n H 2n -Ar1 or unsubstituted, wherein n is 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and heteroaromatic analogs thereof.

[0212] In some embodiments, the organic layer may further include a host, wherein the host includes at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene).

[0213] In some embodiments, the subject may be selected from the group consisting of:

[0214]

[0215]

[0216]

[0217] Its combination.

[0218] In some embodiments, the organic layer may further include a host, wherein the host includes a metal complex.

[0219] In some embodiments, the 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: a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0220] In yet another aspect, an OLED of the present disclosure may further comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.

[0221] In some embodiments, the emission region may contain a ligand L comprising Formula I A Compounds:

[0222]

[0223] Where Z 1 and Z 2 One of them is C and the other is N; K 1 and K 2 Each of the R is independently a direct bond, S or O; Ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; R A represents zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring; X 1 -X 7 Each of is independently N or CR; R and R A At least one of has the following structure:

[0224]

[0225] Where: X 8 -X 15 Each of which is independently N or CR', is bound to X of Formula I 1 -X 7 One of the rings A or X 8 -X 15 A specific one of them is C; the maximum number of N atoms that can be connected to each other in the ring is two; the remaining R and R A Each of R' and R is independently hydrogen, a substituent of Formula II, Formula III, or a substituent selected from the group consisting of general substituents defined herein; B Each of the ligands L is independently hydrogen, or a substituent selected from the group consisting of general substituents defined herein; A The metal M is coordinated by the indicated dashed line; the ligand L A can be linked to other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt and can coordinate with additional ligands; and any two adjacent R, R' or R A May be joined or fused together to form a ring.

[0226] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED), the organic light-emitting device having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the present disclosure.

[0227] In some embodiments, a consumer product comprises an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain a ligand L comprising Formula I as described herein. A of compounds.

[0228] In some embodiments, the consumer product can 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 head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay having a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0229] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an electric 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 electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a light emission mechanism, light is emitted. In some cases, the exciton can be localized on an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0230] Several OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0231] The first OLEDs used emissive molecules that emitted light from a singlet state ("fluorescence"), as disclosed, for example, in US Pat. 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.

[0232] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices", Nature, Vol. 395, 151-154, 1998 ("Baldo-I"); and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence", Appl. Phys. Lett., Vol. 75, Nos. 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.

[0233] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be manufactured by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in US 7,279,704, columns 6-10, which are incorporated by reference.

[0234] More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, 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. Patent 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. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes comprising a composite cathode having a thin layer of a metal (e.g., Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0235] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be manufactured by depositing the layers in order. Because the most common OLED configuration has a cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100 .

[0236] Figure 1 and 2The simple layered structures described in are provided by way of non-limiting examples, and it should 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 the specifically described materials may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that a combination of materials may be used, such as a mixture of a host and a dopant, or more generally, a mixture. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the 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, for example, Figure 1 and 2 Multiple layers of said different organic materials.

[0237] Structures and materials not specifically described may also be used, such as OLEDs containing polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0238] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Pat. No. 6,337,102 to Forrest et al., 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 their entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include 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 make it compatible with a specific deposition method. For example, branched or unbranched substituents such as alkyl and aryl groups, preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons may be used, and 3 to 20 carbons are a preferred range. Materials having asymmetric structures may have better solution processability than materials having symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0239] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from exposure to harmful substances in an environment including moisture, steam and / or gas. The barrier layer can be deposited on a substrate, an electrode, under a substrate, an electrode, or beside a substrate, an electrode, or on any other part (including an edge) of the device. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques, and may include a composition having a single phase and a composition having multiple phases. Any suitable material or material combination may be used for the barrier layer. The barrier layer may be combined with an inorganic compound or an organic compound or both. A preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098, and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymeric material and non-polymeric material constituting the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of polymeric material to non-polymeric material can be in the range of 95:5 to 5:95. The polymeric material and non-polymeric material can 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.

[0240] The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of the electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronic devices and / or power supplies. The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of consumer products, and the consumer products have one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, and the OLED includes a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product containing one or more of one or more light sources and / or a certain type of visual display. Some examples of consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. Various control mechanisms can be used to control devices manufactured according to 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°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0241] More details regarding OLEDs and the definitions set forth above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0242] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0243] 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.

[0244] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent 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.

[0245] In some embodiments, the compound can be an emitting dopant. In some embodiments, the compound can be emitted via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also referred to as E-type delayed fluorescence, see, for example, U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet elimination, or a combination of these processes. In some embodiments, the emitting dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homogeneous (each ligand is the same). In some embodiments, the compound can be mixed (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligand can be all the same. In some other embodiments, at least one ligand is different from other ligands. In some embodiments, each ligand can be different from each other. This is also true in the embodiments where the ligand coordinated to the metal can be connected to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, where coordinating ligands are linked together, in some embodiments all of the ligands may be identical, and in some other embodiments at least one of the linked ligands may be different from the other ligand(s).

[0246] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the compound can be used as a component of an excited complex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The acceptor concentration can be in the range of 0.001% to 100%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0247] According to another aspect, a formulation comprising a compound described herein is also disclosed.

[0248] The OLEDs disclosed herein may 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.

[0249] In another aspect of the present invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

[0250] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also referred to as supramolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but 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 a supramolecule, the compounds of the present invention can also be incorporated into a supramolecular complex without covalent bonds.

[0251] D. Combinations of Compounds of the Disclosure with Other Materials

[0252] The materials described herein as being 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 can be used in combination with a wide variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0253] a) Conductive dopants:

[0254] The charge transport layer can 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 generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

[0255] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0256]

[0257] b)HIL / HTL:

[0258] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0259] Examples of aromatic amine derivatives for use in HIL or HTL include, but are not limited to, the following general structure:

[0260]

[0261] Ar 1 To Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon cyclic compounds: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each Ar may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0262] In one aspect, Ar 1 To Ar 9 Independently selected from the group consisting of:

[0263]

[0264] Where k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 It is NAr 1, O or S; Ar 1 Having the same groups as defined above.

[0265] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0266]

[0267] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0268] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a relative + / Fc coupling has a minimum oxidation potential in solution of less than about 0.6 V.

[0269] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] c) EBL:

[0277] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can produce substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a 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 a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0278] d) Subject:

[0279] 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 host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0280] Examples of metal complexes used as hosts preferably have the following general formula:

[0281]

[0282] Where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104is independently selected from C, N, O, P and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0283] In one aspect, the metal complex is:

[0284]

[0285] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0286] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0287] In one aspect, the host compound contains at least one selected from the following group: a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option in each group may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0288] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0289]

[0290]

[0291] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, 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. X 101 To X 108 Z is independently selected from C (including CH) or N. 101 and Z 102 Independently selected from NR 101 , O or S.

[0292] 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, US2009 0017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, U S20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO200 6114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0293]

[0294]

[0295]

[0296]

[0297]

[0298] e) Other emitters:

[0299] One or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is commonly 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.

[0300] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP201310263, JP4478555, KR1020090133652, KR20120090133653. 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307] f)HBL:

[0308] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0309] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as used in the subjects described above.

[0310] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0311]

[0312] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0313] g)ETL:

[0314] 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 ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0315] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0316]

[0317] Where R 101is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, 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 above. Ar 1 To Ar 3 has a similar definition to Ar mentioned above. k is an integer from 1 to 20. 101 To X 108 is selected from C (including CH) or N.

[0318] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0319]

[0320] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0321] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, and US2009018957. 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0322]

[0323]

[0324]

[0325] h) Charge Generation Layer (CGL)

[0326] In a tandem or stacked OLED, the CGL plays a fundamental role in the performance and consists 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 electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductivity dopants used in the transport layer.

[0327] 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 specific listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may 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.) may also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0328] 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 present invention. For example, other materials and structures may be used to replace many materials and structures described herein without departing from the spirit of the present invention. The present invention as required may therefore include variations of specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories about why the present invention works are not intended to be restrictive.

[0329] E. Experimental Section

[0330] Synthesis of (L79253)-III-(A'3)(B1)(B3)

[0331] Synthesis of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole

[0332] A suspension of 9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole-2-ol (50 g, 143 mmol, 1 eq.), tripotassium phosphate (60.5 g, 285 mmol, 2 eq.), copper(I) iodide (4.07 g, 21.4 mmol, 0.15 eq.), 1,3-dibromobenzene (88 ml, 713 mmol, 5 eq.) and 2-picolinic acid (5.26 g, 42.8 mmol, 0.3 eq.) in dimethyl sulfoxide (713 ml) was bubbled with nitrogen for 50 minutes. The reaction temperature was raised to 120° C. and the reactants were stirred for 18 hours. The reaction mixture was cooled to room temperature and poured into water (3.6 L). The mixture was extracted with ethyl acetate (4×2 L). The combined organic layers were washed with saturated aqueous ammonium chloride solution (3 L), dried over anhydrous sodium sulfate (150 g) and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography eluting with a gradient of 5 to 40% ethyl acetate in hexanes as a grey solid (95% yield).

[0333] Synthetic N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine

[0334] A mixture of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (29.4 g, 58.1 mmol, 1 eq), N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10)benzene-1,2-diamine (20.1 g, 58.1 mmol, 1 eq) and sodium tert-butoxide (8.94 g, 93 mmol, 1.6 eq) in anhydrous toluene (232 ml) was bubbled with nitrogen for 40 minutes. BINAP (2.90 g, 4.65 mmol, 0.08 eq) and tris(dibenzylideneacetone)dipalladium(0) (2.13 g, 2.33 mmol, 0.04 eq) were added. The reaction mixture was bubbled with nitrogen for 15 minutes and then heated at 100°C for 12 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane (300 mL). The resulting mixture was filtered through a pad of celite, rinsed with dichloromethane (750 mL). The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography, eluting with a gradient of 60 to 100% dichloromethane / hexanes to give the product as a light brown solid (75% yield).

[0335] Synthesis of 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

[0336] A 35 wt% solution of deuterium chloride in D2O (8.81 ml, 106 mmol, 1.6 eq) was added dropwise to N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (51 g, 66.1 mmol, 1 eq) in triethyl orthoformate (330 ml). The reaction temperature was raised to 90 °C and the reactants were stirred for 1 hour. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. Toluene (50 mL) was added and the resulting slurry was concentrated under reduced pressure. The residue was triturated with a 1:2 diethyl ether-hexane mixture (450 mL) to give the product as an off-white solid (99% yield).

[0337] Synthesis of 7-(3-(3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4 -Benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II)

[0338] 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A mixture of )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (25.5 g, 32.6 mmol, 1 eq), a platinum precursor (1.1 eq) and a base (3.3 eq) in an organic solvent (652 ml) was bubbled with nitrogen for 40 minutes. The mixture was refluxed for 14.5 hours, cooled to room temperature, and filtered. The filter cake was washed with methanol (100 mL) and dried on the filter to give the crude product (30 g). The crude product was purified by silica gel column chromatography eluting with 80% dichloromethane / hexanes to give the product as a yellow solid (70% yield).

[0339] Synthesis of (L79253)-III-(A'3)(B1)(B3)

[0340] A mixture of allylpalladium chloride dimer (28.2 mg, 0.08 mmol, 0.15 eq) and cBRIDP (54.3 mg, 0.15 mmol, 0.3 eq) was stirred in anhydrous THF (0.5 mL) under nitrogen for 5 min. 7-(3-(3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II) (500 mg, 0.51 mmol, 1.0 equiv) was added followed by anhydrous xylene (2.5 mL) (vial A). In another vial (vial B), 1,8-dimethyl-9H-carbazole (601 mg, 3.08 mmol, 6 equiv) was dissolved in anhydrous THF (0.5 mL) and cooled to 0°C. A 3M solution of methylmagnesium chloride in THF (1.03 mL, 3.08 mmol, 6 equiv) was added under nitrogen. The mixture was stirred at 0°C for 5 minutes. The solution of vial A was added to vial B via a syringe under nitrogen. Vial A was rinsed with xylene (2.5 mL) and added to vial B. The reaction mixture (vial B) was heated at 120°C for 20 hours. After cooling to room temperature, the mixture was diluted with dichloromethane (5 mL) and filtered through a pad of celite. The celite pad was rinsed with additional dichloromethane (3×20 mL). The filtrate was purified by column chromatography, eluting with a gradient of 10%-40% dichloromethane (containing 5% ethyl acetate) / hexanes to give the product as a light yellow solid (41% yield).

[0341] Synthesis of (L79253)-III-(A'4)(B34)(B3)

[0342] Synthetic N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2 -(3-((9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-[1,3'-bicarbazole]-7'-yl)oxy)phenyl)benzene-1,2-diamine

[0343] 7'-(3-bromophenoxy)-9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-1,3'-bicarbazole (400 mg, 0.56 mmol, 1 equivalent), N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10A mixture of benzene-1,2-diamine (233 mg, 0.67 mmol, 1.1 eq.) and sodium tert-butoxide (162 mg, 1.7 mmol, 3 eq.) in toluene (4 mL) was bubbled with nitrogen for 15 minutes. A mixture of allyl palladium chloride dimer (24 mg, 0.06 mmol, 0.1 eq.) and cBRIDP (40 mg, 0.11 mmol, 0.2 eq.) in toluene (2 mL) was bubbled with nitrogen for 15 minutes and transferred to the first mixture via a syringe. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and filtered through a celite pad, which was washed with dichloromethane (0.5 L). The filtrate was concentrated under reduced pressure to give a crude product (99% yield).

[0344] Synthesis of (3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1-(3-((9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-[1,3'-bicarbazole]-7'-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium) chloride

[0345] N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2 A mixture of -(3-((9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-[1,3'-bicarbazole]-7'-yl)oxy)phenyl)benzene-1,2-diamine (549 mg, 1.1 mmol) and 35% deuterium chloride / deuterium oxide (0.8 mL, 9 mmol, 8 equiv) in triethyl orthoformate (15 mL) was refluxed for 18 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto celite and purified by column chromatography eluting with a gradient of 80 to 100% dichloromethane / hexanes followed by 0 to 10% methanol / dichloromethane to give the product (78% yield).

[0346] Synthesis of (L79253)-III-(A'4)(B34)(B3)

[0347] The organic solvent (18 mL) was bubbled with nitrogen for 30 minutes and transferred to a column containing (3-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d 10)-1-(3-((9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-[1,3'-bicarbazole]-7'-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium)chloride (380 mg, 0.37 mmol, 1 eq) and base (3 eq) were added to a round bottom flask. The mixture was bubbled with nitrogen for 15 minutes. Platinum precursor (1 eq) was added and bubbling continued for 5 minutes. The reaction mixture was heated at 60°C for one hour and at 190°C for four days. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto celite and purified by column chromatography eluting with a gradient of 0 to 70% dichloromethane / hexanes to give the product (30% yield).

[0348] Synthesis of (L79253)-III-(A'6)(B34)(B3)

[0349] Synthesis of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole

[0350] A suspension of 9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole-2-ol (50 g, 143 mmol, 1 eq.), tripotassium phosphate (60.5 g, 285 mmol, 2 eq.), copper(I) iodide (4.07 g, 21.4 mmol, 0.15 eq.), 1,3-dibromobenzene (88 ml, 713 mmol, 5 eq.) and 2-picolinic acid (5.26 g, 42.8 mmol, 0.3 eq.) in dimethyl sulfoxide (713 ml) was bubbled with nitrogen for 50 minutes. The reaction temperature was raised to 120° C. and the reactants were stirred for 18 hours. The reaction mixture was cooled to room temperature and poured into water (3.6 L). The mixture was extracted with ethyl acetate (4×2 L). The combined organic layers were washed with saturated aqueous ammonium chloride solution (3 L), dried over anhydrous sodium sulfate (150 g) and concentrated under reduced pressure. The residue was absorbed onto celite and purified by column chromatography system eluting with a gradient of 5 to 40% ethyl acetate in hexanes to give the product as a grey solid (95% yield).

[0351] Synthetic N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2 -(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine

[0352] 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (29.4 g, 58.1 mmol, 1 equivalent), N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A mixture of 1,2-benzene-1,2-diamine (20.1 g, 58.1 mmol, 1 eq.) and sodium tert-butoxide (8.94 g, 93 mmol, 1.6 eq.) in anhydrous toluene (232 ml) was bubbled with nitrogen for 40 minutes. BINAP (2.90 g, 4.65 mmol, 0.08 eq.) and tris(dibenzylideneacetone)dipalladium(0) (2.13 g, 2.33 mmol, 0.04 eq.) were added. The reaction mixture was bubbled with nitrogen for 15 minutes and then heated at 100 °C for 12 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane (300 mL). The resulting mixture was filtered through a pad of celite, rinsed with dichloromethane (750 mL). The filtrate was concentrated under reduced pressure, and the residue was taken up on celite (150 g). The crude product was purified by column chromatography eluting with a gradient of 60 to 100% dichloromethane / hexanes to afford the product as a light brown solid (75% yield).

[0353] Synthesis of 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

[0354] A 35 wt% solution of deuterium chloride in D2O (8.81 ml, 106 mmol, 1.6 eq) was added dropwise to N 1 -([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N 2 -(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (51 g, 66.1 mmol, 1 eq) in triethyl orthoformate (330 ml). The reaction temperature was raised to 90 °C and the reaction was stirred for 1 hour. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was triturated with a 1:2 diethyl ether-hexane mixture (450 mL) to give the product as an off-white solid (99% yield).

[0355] Synthesis of 7-(3-(3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4 -Benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II)

[0356] 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A mixture of )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (25.5 g, 32.6 mmol, 1 eq), platinum precursor (1.1 eq) and base (3.3 eq) in solvent (652 ml) was bubbled with nitrogen for 40 minutes. The mixture was refluxed for 14.5 hours, cooled to room temperature, and filtered. The crude product was absorbed onto celite and purified by column chromatography eluting with 80% dichloromethane / hexanes to give the product as a yellow solid (70% yield).

[0357] Synthesis of (L79253)-III-(A'6)(B34)(B3)

[0358] 7-(3-(3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4 A solution of 4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II) (800 mg, 0.82 mmol, 1.0 equiv), tripotassium phosphate monohydrate (756 mg, 3.28 mmol, 4.0 equiv), (9-phenyl-9H-carbazole-3-yl)boronic acid (943 mg, 3.28 mmol, 4.0 equiv) and SPhos-Pd-G2 (59.2 mg, 0.08 mmol, 0.1 equiv) in a 10:1 mixture of dioxane and water (8.8 mL) was bubbled with nitrogen for 15 minutes. The reaction mixture was heated at 100 °C for 18 hours. The crude mixture was cooled to room temperature and filtered through a pad of celite. The crude material was absorbed onto celite and purified by column chromatography eluting with 30% dichloromethane / hexanes to give the product as a light yellow solid (41% yield).

[0359] Synthesis of (L79253)-III-(A'1)(B41)(B3)

[0360] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-7-methoxy-9H-3,9'-bicarbazole

[0361] A solution of tris(dibenzylideneacetone)dipalladium(0) (3.1 g, 3.4 mmol, 0.09 equiv) and tri-tert-butylphosphonium tetrafluoroborate (1.97 g, 6.79 mmol, 17.2 equiv) in toluene (400 mL) was bubbled with nitrogen for 20 minutes, followed by the addition of 9H-carbazole (7.0 g, 42 mmol, 1.1 equiv), 9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-2-methoxy-9H-carbazole (15.8 g, 39.4 mmol, 1.00 equiv) and additional toluene (450 mL). The mixture was bubbled with nitrogen for an additional 10 minutes, and then treated with sodium tert-butoxide (11.9 g, 124 mmol, 3.14 equiv) added portionwise over one minute. The reaction mixture was heated at 111° C. for 17 hours, and then cooled to room temperature. The mixture was filtered through celite and the filter pad was washed with toluene (1 L). The filtrate was washed with water (2 x 500 mL), saturated brine (500 mL), dried over sodium sulfate (30 g). The crude product was absorbed onto celite and purified by column chromatography eluting with a gradient of 0 to 10% ethyl acetate in heptane to give the product as a light tan foam (69% yield).

[0362] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-ol

[0363] A mixture of 9-(4-(tert-butyl)pyridin-2-yl)-7-methoxy-9H-3,9'-bicarbazole (14.4 g, 29.0 mmol, 1.00 equiv) in 48% HBr (440 mL, 656 g, 8.11 mol, 280 equiv) was heated at reflux for 16 hours. The mixture was cooled to room temperature, neutralized with solid sodium bicarbonate (450 g), partitioned between water (200 mL) and ethyl acetate (500 mL), and the layers were separated. The aqueous layer was extracted with ethyl acetate (400 mL). The combined organic layers were washed with saturated sodium chloride (300 mL), dried over sodium sulfate (50 g), and the residue was adsorbed onto celite and purified by column chromatography, eluting with a gradient of 0 to 25% ethyl acetate / heptane to give the product as an off-white solid (76% yield).

[0364] Synthesis of 7-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole

[0365] A mixture of 9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-ol (13.9 g, 28.9 mmol, 1.00 equiv), 1,3-dibromobenzene (20.9 g, 88.6 mmol, 3.07 equiv) and picolinic acid (0.43 g, 3.5 mmol, 0.12 equiv) in dimethyl sulfoxide (140 mL) was bubbled with nitrogen for 15 minutes at room temperature. Potassium phosphate (12.9 g, 90.8 mmol, 2.10 equiv) was added, and the mixture was bubbled with nitrogen for five minutes. Copper (I) iodide (0.33 g, 1.7 mmol, 0.06 equiv) was added. The mixture was bubbled with nitrogen for five minutes and then heated at 120°C for 21 hours. The reaction mixture was cooled to room temperature and distributed between methyl tert-butyl ether (250 mL) and 28-30% aqueous ammonium hydroxide solution (240 mL) and water (220 mL). The layers were separated and the aqueous layer was extracted with methyl tert-butyl ether (2×250 mL). The combined organic layers were washed with water (2×250 mL), 28-30% aqueous ammonium hydroxide solution (200 mL) and saturated brine (250 mL). The organic layer was dried over sodium sulfate (10 g), concentrated under reduced pressure, and absorbed onto diatomaceous earth. The crude product was purified by column chromatography, eluting with a gradient of 0 to 10% ethyl acetate / heptane to give the product as a heterogeneous yellow and white solid (53% yield).

[0366] Synthesis of N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-yl)oxy)phenyl)benzene-1,2-diamine

[0367] A mixture of allylpalladium chloride dimer (386 mg, 1.05 mmol, 0.060 equiv) and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (cBRIDP, 753 mg, 2.14 mmol, 1.22 equiv) in toluene (50 mL) was bubbled with nitrogen for 25 min while heating to 80° C. to give a yellow solution. Separately, N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d 10A mixture of 2-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole (11.7 g, 18.4 mmol, 1.05 equiv) and sodium tert-butoxide (5.28 g, 54.9 mmol, 3.14 equiv) in toluene (300 mL) was bubbled with nitrogen for 15 minutes while heating to 85 °C. The catalyst solution was transferred to the reagent mixture at 85 °C. The combined mixture was bubbled with nitrogen for five minutes at 85 °C and then heated at 111 °C for eight hours. The mixture was cooled to room temperature and diluted with water (200 mL). The biphasic mixture was filtered through celite. The filter pad was washed with ethyl acetate (500 mL) and the filtrate layers were separated. The organic layer was washed with water (500 mL) and saturated brine (400 mL), dried over sodium sulfate (80 g) and concentrated under reduced pressure to a black foam (18.9 g). The residue was absorbed onto celite and purified by column chromatography, eluting with a gradient of 0 to 25% ethyl acetate in heptane to give the product as a brown solid (75% yield).

[0368] Synthesis of 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

[0369] N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A solution of )-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-yl)oxy)phenyl)benzene-1,2-diamine (12.5 g, 13.9 mmol, 1.00 equiv) in triethyl orthoformate (75 mL) was treated with concentrated hydrochloric acid (2.0 mL, 24 mmol, 1.7 equiv). The mixture was stirred at room temperature for one hour and then at 80 °C for six hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, and then concentrated from ethanol (75 mL) to give a red / brown residue (18.7 g) which was absorbed onto silica gel. The residue was purified by column chromatography eluting with a gradient of 0 to 10% methanol in dichloromethane to give the product as a light tan foam (70% yield).

[0370] Synthesis of (L79253)-III-(A'1)(B41)(B3)

[0371] 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A solution of )-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-7-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (9.18 g, 9.68 mmol, 1.0 equiv) in an organic solvent (200 mL) was bubbled with nitrogen for ten minutes. The solution was treated with base (3.33 equiv) and bubbled with nitrogen for 15 minutes at room temperature. The reaction was treated with a platinum precursor (1.01 equiv), bubbled with nitrogen for five minutes, then heated at 110°C for 32 hours. The reaction was cooled to room temperature and concentrated under reduced pressure. The residue was absorbed onto celite and purified by column chromatography eluting with 55% dichloromethane / hexanes. The product was triturated in methanol (230 mL) at 26 °C for 70 min, filtered and washed with methanol (100 mL) to give the product as a yellow solid (41% yield).

[0372] Synthesis of (L79221)-III-(A'6)(B34)(B3)

[0373] Synthesis of (L79221)-III-(A'6)(B34)(B3)

[0374] A solution of 7'-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9'-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9'H-1,3'-bicarbazole (3.00 g, 3.35 mmol, 1.00 equiv) and silver(I) oxide (390 mg, 1.7 mmol, 0.50 equiv) in 1,2-dichloroethane (120 mL) was bubbled with nitrogen for 20 minutes in the absence of light, then stirred at room temperature for 3 days. The mixture was concentrated under reduced pressure. 1,2-Dichlorobenzene (120 mL) and dichloro(1,5-cyclooctadiene)platinum(II) (1.25 g, 3.35 mmol, 1.00 equiv) were added, and the suspension was bubbled with nitrogen for 20 minutes. The mixture was stirred at reflux for 26 hours in the absence of light. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was absorbed onto celite and purified by column chromatography eluting with 50% dichloromethane / hexanes.The product fractions were triturated in methanol (80 mL) at room temperature for 3 hours then filtered to give the product as a yellow solid (57% yield).

[0375] Synthesis of (L79221)-III-(A'1)(B41)(B3)

[0376] Synthesis of (L79221)-III-(A'1)(B41)(B3)

[0377] 7-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole (2.5 g, 3.05 mmol, 1.0 equiv) was stirred in 1,2-dichloroethane (120 mL) at room temperature until completely dissolved. Silver(I) oxide (0.352 g, 1.52 mmol, 0.5 equiv) was added and the mixture was stirred overnight in the dark. The mixture was concentrated under reduced pressure and the residue was dissolved in 1,2-dichlorobenzene (120 mL). The solution was bubbled with nitrogen for 5 minutes, and dichloro(1,5-cyclooctadiene)platinum(II) (1.14 g, 3.05 mmol, 1.0 equiv) was added. The mixture was heated under vigorous reflux overnight, at which time LC / MS analysis indicated that the reaction was complete. The mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was dry loaded onto celite and purified by column chromatography eluting with 60% dichloromethane / hexanes to give a yellow solid. The purified compound was triturated with methanol (100 mL) and dried at 50 °C in vacuo for 18 h to give the product as a yellow solid (37% yield).

[0378] Synthesis of 3-bromo-2-methoxy-9H-carbazole

[0379] A solution of 2-methoxy-9H-carbazole (20.1 g, 102 mmol, 1.00 equiv) and N-bromosuccinimide (18.1 g, 102 mmol, 1.00 equiv) in dichloromethane (1 L) was stirred at room temperature for 18 hours. The reaction mixture was washed with saturated aqueous ammonium chloride (2 x 800 mL) and saturated brine (800 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto celite and purified by column chromatography eluting with a gradient of 0 to 50% ethyl acetate in heptane to give the product as a white solid (88% yield).

[0380] Synthesis of 3-bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole

[0381] A mixture of 3-bromo-2-methoxy-9H-carbazole (25.1 g, 91.0 mmol, 1.00 equiv) and 2-bromo-4-(tert-butyl)pyridine (20.4 g, 95.3 mmol, 1.05 equiv) in toluene (500 mL) was bubbled with nitrogen for five minutes. 1-Methyl-N-imidazole (7.25 mL, 7.46 g, 91.0 mmol, 1.00 equiv), lithium tert-butoxide (15.3 g, 191 mmol, 2.1 equiv) and copper (I) iodide (6.97 g, 37.0 mmol, 0.40 equiv) were added, and the mixture was bubbled with nitrogen for five minutes, then heated at reflux for 18 hours. The reaction mixture was cooled to room temperature, partitioned between ethyl acetate (300 mL) and 28-30% aqueous ammonium hydroxide solution (200 mL), and the layers were separated. The organic layer was washed with 28-30% aqueous ammonium hydroxide solution (3 × 200 mL). The aqueous layer was extracted with ethyl acetate (700 mL). The combined organic layer was washed with saturated brine (500 mL), dried over sodium sulfate, and concentrated under reduced pressure. The residue was absorbed onto diatomaceous earth and purified by column chromatography, eluting with a gradient of 0 to 10% ethyl acetate / heptane to give 3-bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole and 3-iodo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole as yellow and white heterogeneous solids: 2: 1 mixture (75% yield).

[0382] Synthesis of N-(9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide

[0383] A mixture of 3-bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole and 3-iodo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole (31.5 g, 72.8 mmol, 1.00 equiv) in toluene (750 mL) was bubbled with nitrogen for 30 minutes, and acetamide (22.8 g, 386 mmol, 5.02 equiv), potassium carbonate (22.6 g, 164 mmol, 2.25 equiv), 1,2-diaminocyclohexane (9.25 mL, 8.80 g, 77.0 mmol, 1.06 equiv) and copper (I) iodide (3.60 g, 18.9 mmol, 0.26 equiv) were added. The mixture was bubbled with nitrogen for five minutes and heated to 111° C. for four days. The reaction mixture was cooled to room temperature, treated with water (500 mL), then filtered through diatomaceous earth (160 g), rinsed with ethyl acetate (1.5 L) and water (500 mL). The two-phase filtrate layer was separated and the aqueous layer was extracted with ethyl acetate (500 mL). The combined organic layer was washed with 10% aqueous ammonium hydroxide solution (2×300 mL), water (500 mL) and saturated brine (500 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto diatomaceous earth and purified by column chromatography, eluting with a gradient of 20 to 100% ethyl acetate / heptane to give the product as an off-white solid (83% yield).

[0384] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole-3-amine

[0385] A solution of N-(9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole-3-yl)acetamide (25.6 g, 66.1 mmol, 1.00 equiv) in 2-propanol (600 mL) was treated with a solution of potassium hydroxide (157 g, 2.80 mol, 42 equiv) in water (75 mL) at 80 °C for 22 hours. The mixture was cooled to room temperature and the layers were separated. The organic layer was concentrated under reduced pressure to a minimum volume. The aqueous layer was extracted with ethyl acetate (500 mL). The combined organics were washed with saturated brine (400 mL), dried over sodium sulfate, and concentrated under reduced pressure to give a black foam (23.5 g). The residue was absorbed onto celite and purified by column chromatography, eluting with a gradient of 10 to 25% ethyl acetate / heptane to give the product as a brown solid (83% yield).

[0386] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole-3-amine

[0387] A mixture of 9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole-3-amine (20.0 g, 57.9 mmol, 1.00 equiv) and 2,2'-dibromo-1,1'-biphenyl (19.9 g, 63.8, 1.10 equiv) in xylene (1.1 L) was bubbled with nitrogen for 20 minutes at room temperature. The mixture was treated with sodium tert-butoxide (11.8 g, 123 mmol, 2.10 equiv) and bubbled with nitrogen for an additional 20 minutes while heating to 90°C. Separately, a mixture of tris(dibenzylideneacetone)dipalladium(0) (3.18 g, 3.47 mmol, 0.06 equiv) and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhos, 2.87 g, 6.99 mmol, 0.12 equiv) in xylene (100 mL) was bubbled with nitrogen for 30 minutes while heating to 90°C. The catalyst mixture (at 90°C) was poured directly into the reagent mixture (at 90°C), which was bubbled with nitrogen for 10 minutes and then heated at 111°C for 18 hours. The mixture was cooled to room temperature and diluted with water (1 L) under vigorous stirring. The two-phase mixture was filtered through diatomaceous earth (100 g) and washed with ethyl acetate (1 L). The filtrate layers were separated. The organic layer was washed with saturated brine (1 L), dried over sodium sulfate, and concentrated under reduced pressure to give a brown oil. The residue was absorbed onto celite and purified by column chromatography eluting with a gradient of 0 to 25% ethyl acetate in heptane to give the product as a red oil (92% yield).

[0388] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-2-ol

[0389] A solution of 9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole-3-amine (27 g, 55 mmol, 1.00 equiv) and sodium ethanethiolate (13.8 g, 163 mmol, 3.0 equiv) in N-methyl-2-pyrrolidone (400 mL) was heated at 130 °C for 18 hours. The reaction mixture was cooled to room temperature and diluted with saturated aqueous ammonium chloride (400 mL) and ethyl acetate (250 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (250 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate (2 x 250 mL) and saturated brine (500 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto celite and purified by column chromatography, eluting with a gradient of 0 to 20% ethyl acetate / heptane to give the product as a light brown solid (92% yield).

[0390] Synthesis of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole

[0391] A mixture of 9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-2-ol (24.9 g, 51.7 mmol, 1.00 equiv) and 1,3-dibromobenzene (24.0 g, 102 mmol, 1.97 equiv) in dimethyl sulfoxide (300 mL) was bubbled with nitrogen for 30 minutes while picolinic acid (0.75 g, 6.1 mmol, 0.12 equiv), tripotassium phosphate (22.7 g, 107 mmol, 2.07 equiv) and copper (I) iodide (0.58 g, 3.1 mmol, 0.06 equiv) were added. The mixture was heated at 120 °C for 47 hours. The reaction mixture was cooled to room temperature and diluted with methyl tert-butyl ether (250 mL) and 10% aqueous ammonium hydroxide solution (250 mL). The layers were separated and the organic layer was washed with 10% aqueous ammonium hydroxide solution (2×250 mL). The combined aqueous layers were extracted with methyl tert-butyl ether (250 mL). The combined organic layers were washed with saturated brine (500 mL), dried over sodium sulfate, and concentrated under reduced pressure to give a black oil. The residue was absorbed onto celite and purified by column chromatography system, eluting with a gradient of 5 to 50% dichloromethane / heptane to give the product as a dark yellow solid (49% yield).

[0392] Synthesis of N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-2-yl)oxy)phenyl)benzene-1,2-diamine (DSC-2020-698-1)

[0393] N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10A mixture of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole (0.5 g, 0.785 mmol, 1.0 equiv) and sodium tert-butoxide (0.266 g, 2.356 mmol, 3 equiv) in toluene (8 mL) was bubbled with nitrogen for 15 minutes. A mixture of tris(dibenzylideneacetone)dipalladium(0) (29 mg, 0.031 mmol, 0.04 equiv) and BINAP (39 mg, 0.063 mmol, 0.08 equiv) in toluene (1 mL) was bubbled with nitrogen for 15 minutes and transferred to the first mixture via a syringe. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto celite and purified by column eluting with a gradient of 10 to 30% ethyl acetate in hexanes to give the product as a white solid (71% yield).

[0394] Synthesis of 2-(3-(1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4 -Benzo[d]imidazol-3-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole

[0395] N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A mixture of )-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9'-bicarbazole]-2-yl)oxy)phenyl)benzene-1,2-diamine (5.0 g, 5.54 mmol, 1 eq) and 35% deuterium chloride / deuterium oxide (0.9 mL, 22.17 mmol, 4 eq) in triethyl orthoformate (37 mL) was refluxed for 18 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto celite and purified by column chromatography eluting with a gradient of 0 to 10% methanol / dichloromethane to give the product (65% yield).

[0396] Synthesis of (L79253)-VI-(A'1)B41)(B3)

[0397] The 2-(3-(1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-1H-3λ 4-benzo[d]imidazole-3-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9'-bicarbazole (0.1 g, 0.11 mmol, 1.0 equiv) and platinum precursor (59 mg, 0.142 mmol, 1.3 equiv) in an organic solvent (3 mL) were bubbled with nitrogen for 15 minutes. Base (47 mg, 0.438 mmol, 4.0 equiv) was added to the reaction mixture in one portion. The reaction mixture was heated at 130 °C for 16 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in dichloromethane (20 mL), absorbed onto diatomaceous earth, and purified by column chromatography eluting with 50% dichloromethane / hexanes. The product was concentrated under reduced pressure and dried in a vacuum oven at 50 °C for 18 hours to a light yellow solid (40% yield).

[0398] It is believed that Formula I and Formula II of the present disclosure produce narrow blue emission and can be used for narrow and deep blue in OLED devices. Table 1 below shows some photoluminescent properties of some representative compounds of the present disclosure. It can be seen that these compounds have a peak wavelength of less than 460nm and a full width at half maximum (FWHM) of less than 21nm. The emission spectrum was obtained on a film of the compound in polymethyl methacrylate (PMMA) using a HamamatsuQuantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer with an excitation wavelength of 340nm. The film was prepared by generating a solution of less than 1% emitter with toluene containing PMMA, which was prepared, filtered and drop-coated onto a quartz substrate.

[0399] Table 1

[0400]

[0401]

[0402] OLEDs were made from several representative compounds and found to be narrow, with a FWHM below 30 nm. In addition, the OLED device achieved a deep blue color at a 1931 CIE y of less than 0.160. Typically, the FWHM of the conversion phosphorescent emitter complex is above 60 nm. Achieving a small FWHM is a goal that has been pursued. The smaller the FWHM, the better the color purity for display applications. As background information, the ideal line shape is a single wavelength (single line). As can be seen here, the compounds of the present invention can cut more than half the number of FWHMs from the conversion phosphorescent emitter. In past OLED research, narrowed emission line shapes have been achieved nanometer by nanometer, and the substantial reduction in FWHM obtained from these compounds of the present invention is a significantly unexpected result.

[0403] OLEDs were grown on glass substrates pre-coated with an indium tin oxide (ITO) layer with a 15-Ω / sq sheet resistance. Prior to any organic layer deposition or coating, the substrates were degreased with solvent and then treated with oxygen plasma at 50 W at 100 mTorr for 1.5 min and UV ozone for 5 min.

[0404] The device in Table 2 was produced by thermal evaporation in a high vacuum (<10 -6 The anode electrode is Starting from the ITO surface, the device example has organic layers consisting of: Compound 1 (HIL), Compound 2 (HTL), Compound 3 (EBL), Compound 4 doped with 20% compound 4, 5% compound 3 and 10% emitter 1 (EML), Compound 5 (BL), Compound 6 doped with 35% of compound 7 (ETL), Compound 6 (EIL), followed by of Al (cathode). All devices were immediately packaged in a nitrogen glove box (<1 ppm of H2O and O2) with epoxy-sealed glass lids after fabrication, with a moisture getter incorporated inside the package. Doping percentages are by volume.

[0405]

[0406] The compounds used to make OLED devices are the following:

[0407]

Claims

1. A compound having the following structure in: Z 2 C and Z 1 is N; R A indicates zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring; X 1 -X 6 Each of is independently N or CR; At least one of R has the following structure: Formula II or Formula III Where: X 8 -X 15 Each of which is independently N or CR', bonded to X 1 -X 6 One of them is C; The maximum number of N atoms that can be connected to each other within the ring is two; Each of the remaining R is independently hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, amino, silanyl, alkenyl, aryl, nitrile, isonitrile, and combinations thereof; R A Each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, amino, silane, alkenyl, aryl, nitrile, isonitrile, and combinations thereof; R' and R B Each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, amino, silanyl, alkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; L 2 Independently selected from the group consisting of: O and S; R C and R D Each represents zero substitution, single substitution, or up to the maximum allowed number of substitutions on its associated ring; R C and R D Each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, amino, silane, alkenyl, aryl, nitrile, isonitrile, and combinations thereof; R X is selected from the group consisting of: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; and Any two adjacent R, R', R A , R B , R C or R D They may be linked or fused together to form a ring where chemically feasible.

2. The compound of claim 1, wherein each of the remaining R's is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, amino, silanyl, alkenyl, aryl, nitrile, isonitrile, and combinations thereof.

3. The compound according to claim 1, wherein X 1 -X 6 Each is CR, and X 8 -X 15 Each is independently C or CR'.

4. The compound according to claim 1, wherein X 1 -X 6 and X 8 -X 15 One of them is N, and X 1 -X 6 and X 8 -X 15 The rest of X 1 -X 6 For each is CR, and for X 8 -X 15 are independently C or CR'.

5. The compound according to claim 1, wherein X 1 -X 6 and X 8 -X 15 Two of them are N, and X 1 -X 6 and X 8 -X 15 The rest of X 1 -X 6 For each is CR, and for X 8 -X 15 are independently C or CR'.

6. The compound according to claim 1, wherein X 1 -X 6 One of them is N, X 8 -X 15 One of them is N, and X 1 -X 6 and X 8 -X 15 The rest of X 1 -X 6 For each is CR, and for X 8 -X 15 are independently C or CR'.

7. The compound according to claim 1, wherein the compound comprises the following ligand L A : Formula IV Or V 8. The compound of claim 1, wherein the compound is selected from the group consisting of:

9. The compound according to claim 1, wherein the compound is selected from the group consisting of: compound (I)-I-(A'i)(Bj)(Bk) to compound (I)-XIV-(A'i)(Bj)(Bk), each having the formula Pt(L A )(L B ), the formula has the following structure: Where L A Having the structure shown above and selected from the group consisting of: I-(A'i)(Bj)(Bk) to XIV-(A'i)(Bj)(Bk), wherein i is an integer from 1 to 7 and k is an integer from 1 to 47, and when i=1 to 3, j is an integer from 1 to 41, and when i=4 to 7, j is an integer from 1 to 47; Where L B Having the structure shown above and selected from the group consisting of L1; Wherein l is an integer from 1 to 230107; wherein Ring C and D are as defined above for Formula VI; or The compound may be selected from the group consisting of compounds [I-(A'i)(Bj)(Bk)][I-(A'm)(Bn)(Bo)] to compounds [XIV-(A'i)(Bj)(Bk)][XIV-(A'm)(Bn)(Bo)], each having a formula of Pt(L A )(L C ), The formula has the following structure: Where L A As defined above; Where L C having the structure shown above and selected from the group consisting of: I-(A'm)(Bn)(Bo) to XIV-(A'm)(Bn)(Bo); wherein L1 independently at each occurrence has the structure defined in the following table: Each wavy line in each structure is independently used to connect to L A The relevant part: Where A1 to A30 have the following structure: And wherein R1 to R330 have the following structure: And among them L A and L C Independently has the structure defined in the following table: Where A'1 to A'7 have the following structure: Among them, B1 to B47 have the following structures:

10. A compound selected from the group consisting of:

11. An organic light emitting device (OLED), comprising: anode; cathode; and an organic layer disposed between the anode and the cathode, The organic layer contains the compound according to any one of claims 1 to 10.

12. The OLED of claim 11, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

13. The OLED of claim 12, wherein the host is selected from the group consisting of: and combinations thereof.

14. A consumer product comprising an organic light emitting device (OLED), wherein the OLED comprises: anode; cathode; and an organic layer disposed between the anode and the cathode, The organic layer contains the compound according to any one of claims 1 to 10.

15. A formulation comprising a compound according to any one of claims 1-10.

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