Organic electroluminescent materials and devices

Abstract

The present application relates to organic electroluminescent materials and devices. Provided are organometallic compounds of the formula A I, or Formula II, comprising a ligand L of the formula Also provided are formulations comprising these organometallic compounds. Further provided are OLEDs and related consumer products utilizing these organometallic compounds.

Description

[0001] This application is a divisional application of the application filed on October 8, 2021, with application number 202111172913.8 and invention title "Organic Electroluminescent Material and Device".

[0002] This application claims priority to U.S. Provisional Application No. 63 / 087,062, filed October 2, 2020, and U.S. Provisional Application No. 63 / 193,755, filed May 27, 2021, pursuant to 35 USC § 119(e), the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to organometallic compounds and formulations and their various uses, including as emitters in devices such as organic light-emitting diodes and related electronic devices. Background Technology

[0004] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suited to emitting specific colors (called "saturated" colors). Specifically, these standards require pixels saturated with red, green, and blue light. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single-emitting-layer (EML) devices or stacked structures. Color can be measured using the CIE coordinate system, well-known in the field. Summary of the Invention

[0007] In one aspect, this disclosure provides a ligand L comprising the following formula: A compounds

[0008] Formula I , or Formula II ,

[0009] Among them, ring A is an independent 5- to 10-membered heterocyclic ring; X 1 To X 6 Each is independently C or N; K 3 It is a direct bond, O or S; the maximum number of N atoms connected to each other within the ring is two; R A R B and R C Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein, wherein the ligand L A It complexes with metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and any two adjacent R A R B R C or R 1 The compounds may connect or fuse to form rings, provided that the compounds do not contain any of the structures shown below:

[0010] or .

[0011] In another aspect, this disclosure provides ligands L comprising Formula I or Formula II as described herein. A Compound formulations.

[0012] In yet another aspect, this disclosure provides an OLED having an organic layer comprising a ligand L of formula I or formula II as described herein. A Compounds.

[0013] In yet another aspect, this disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound containing a ligand L of formula I or II as described herein. A . Attached Figure Description

[0015] Figure 1 An organic light-emitting device is shown.

[0016] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated. Detailed Implementation

[0017] A. Terminology

[0018] Unless otherwise specified, the following terms as used herein are defined as follows:

[0019] As used herein, the term "organic" includes both polymeric materials and small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist 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. Dendritic polymers can be "small molecules," and all dendritic polymers currently used in the OLED field are considered small molecules.

[0020] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "above" the second layer, the first layer is placed further away from the substrate. Unless specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "above" the anode.

[0021] As used herein, “solution-handleable” means capable of dissolving, dispersing or transporting in and / or depositing from a liquid medium in the form of a solution or suspension.

[0022] When a ligand is considered to directly contribute to the photosensitivity of the emissive material, the ligand may be referred to as "photosensitive." When a ligand is considered not to contribute to the photosensitivity of the emissive material, the ligand may be referred to as "auxiliary," but auxiliary ligands can alter the properties of photosensitizing ligands.

[0023] As used herein, and as will generally be understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) level is "greater than" or "higher than" the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, the LUMO levels of a material are higher than the HOMO levels of the same material. A "higher" HOMO or LUMO level appears to be closer to the top of this diagram than a "lower" HOMO or LUMO level.

[0024] As used herein, and as will generally be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0025] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0026] The term "acyl" refers to the substituted carbonyl group (C(O)-R). s ).

[0027] The term "ester" refers to the substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0028] The term "ether" refers to -OR s Group.

[0029] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0030] The term "selenyl" refers to -SeR 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 "phosphin" refers to -P(R) s )3 groups, wherein each R s They can be the same or different.

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

[0035] The term "germanium alkyl" refers to -Ge(R) s )3 groups, wherein each R s They can be the same or different.

[0036] The term "boronyl" refers to -B(R s )2 group or its Lewis adduct -B(R s )3 groups, of which R s They can be the same or different.

[0037] In each of the above, R s It can be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s Choose from the following groups: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0038] The term "alkyl" refers to and includes both straight-chain and branched 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. Additionally, the alkyl group may optionally be substituted.

[0039] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, the cycloalkyl group may optionally be substituted.

[0040] The terms "heteroalkyl" or "heterocyclic alkyl" refer to alkyl or cycloalkyl groups having at least one carbon atom substituted with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocyclic alkyl group may optionally be substituted.

[0041] The term "alkenyl" refers to and includes both straight-chain and branched alkenyl groups. An alkenyl group is essentially an alkyl group comprising at least one carbon-carbon double bond in an alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising at least one carbon-carbon double bond in a cycloalkyl ring. The term "heteroalkenyl" as used herein 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. Additionally, alkenyl, cycloalkenyl, or heteroalkenyl groups may optionally be substituted.

[0042] The term "alkynyl" refers to and includes both straight-chain and branched alkynyl groups. An alkynyl group is essentially an alkyl group comprising at least one carbon-carbon triple bond in an alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0043] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group that has been substituted with an aryl group. Additionally, aralkyl groups may optionally be substituted.

[0044] 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 are used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group may be optionally substituted.

[0045] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. A polycyclic system may have two or more rings in which two carbons are shared by 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, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, β-, perylene, and azulene, with phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene being preferred. Additionally, the aryl group may optionally be substituted.

[0046] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems comprising 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 having 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic systems may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole-carbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazole Phosphorus, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selelenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazynylene, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0047] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, as well as their respective aza analogs, are of particular interest.

[0048] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocycloyl, aryl, and heteroaryl are either unsubstituted or substituted independently by one or more common substituents.

[0049] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronalkyl, and combinations thereof.

[0050] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0051] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boroalkyl, aryl, heteroaryl, thio, and combinations thereof.

[0052] In other cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0053] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing a single substitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen with available valences in the ring atom, such as the carbon atom in benzene and the nitrogen atom in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0054] As used herein, “combination thereof” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents; and halogen, alkyl, and aryl groups can be combined to form haloaralkyl groups. In one instance, the term substitution includes a combination of two to four listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, 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 containing up to forty atoms that are not hydrogen or deuterium, or combinations containing 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.

[0055] The term "aza" in the passages described herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., refers to the fact that one or more of the CH groups in the corresponding aromatic ring can be replaced by nitrogen atoms, for example and without any limitation. Azatribenzene encompasses dibenzo[ f,h Quinoxaline and dibenzo[ f,h Quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily apparent to those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0056] As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US 2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angewandte Chemie International Edition (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entirety) describe efficient pathways for the deuteration of methylene hydrogen in benzylamine and the replacement of aromatic cyclic hydrogens with deuterium.

[0057] It should be understood that when a molecular fragment is described as a substituent or additionally linked to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linked fragments are considered equivalent.

[0058] In some cases, a pair of adjacent substituents may optionally join or fuse into a ring. Preferred rings are five-, six-, or seven-membered carbon rings or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved may be adjacent to each other on the same ring, or on two neighboring rings having two closest available substituted positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene), provided that a stable fused ring system can be formed.

[0059] B. Compounds disclosed herein

[0060] In one aspect, this disclosure provides a ligand L comprising the following formula: A compounds

[0061] Formula I , or Formula II ,

[0062] in:

[0063] Ring A is independently a 5- to 10-membered heterocyclic ring;

[0064] X 1 To X 6 Each can be either C or N independently;

[0065] K 3 It is a direct bond, O, or S;

[0066] The maximum number of N atoms connected to each other within the ring is two;

[0067] R A R B and R C Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and

[0068] R1, R A R B R C Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof.

[0069] in:

[0070] The ligand L A It is connected to metal M via two designated dashed lines;

[0071] M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and may optionally coordinate with other ligands;

[0072] The ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0073] Any two adjacent R A R B R C or R 1 They can connect or fuse to form rings.

[0074] The condition is that the compound does not contain any of the structures shown below:

[0075] or .

[0076] In some embodiments, R1, R A and R B Each of them can be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0077] In some embodiments, X 1 To X 3 Each can be C. In some embodiments, X 4 To X 6 Each can be C. In some embodiments, X 1 To X 6 Each of them is C.

[0078] In some embodiments, two adjacent R A Substituents can connect to form a ring fused with ring A. In some embodiments, when ring A is a 7-membered, 8-membered, 9-membered, or 10-membered ring, four adjacent R... A Substituents can connect to form two rings fused with ring A. In some embodiments, when ring A is an octet, quintet, or decaquinet, there are a total of 6 adjacent Rs. A Substituents may connect to form three separate rings, each fused to ring A. In some embodiments, the fused rings may each be independently a 5- or 6-membered aromatic ring. In some embodiments, the fused rings may each be independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, the fused rings may each be independently benzene or imidazole. In some embodiments, all fused rings may be benzene.

[0079] In some embodiments, one R1 substituent of Formula I is combined with one RB Substituents can be linked to form a ring. In some embodiments, one R1 substituent in Formula I is linked to one R... A Substituents can connect to form a ring. In some embodiments, one R in Formula II... C Substituents with an R B Substituents can connect to form a ring. In some embodiments, one R in Formula II... C Substituents with an R A Substituents can connect to form a ring. In some embodiments, two adjacent R groups... B Substituents can connect to form a fused ring. In some embodiments, two adjacent R... C Substituents can connect to form fused rings.

[0080] In some embodiments, ligand L A You can choose from the following groups:

[0081] , , , , , , , , and ,

[0082] Among them, ring A1 is independently a 5- to 10-membered heterocyclic ring; rings A2, A3, A4, A5, B2 and B3 are each independently a 5- or 6-membered carbon ring or heterocyclic ring; and ring B1 is independently a 5-, 6- or 7-membered carbon ring or heterocyclic ring.

[0083] In some embodiments, ligand L A You can choose from the following groups:

[0084] , , , , , , , , , , , ,

[0085] , , , ,

[0086] and ,

[0087] Each Q is independently C or N; and each W is independently BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO2, C=CRR', CRR', SiRR' or GeRR', wherein R and R' are each independently hydrogen or a substituent selected from the group of universal substituents defined herein.

[0088] In some embodiments, ligand L A It can be In some embodiments, ligand L A It can be , where R A1 R A2 and R A3 Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R A1 R A2 and R A3 Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein.

[0089] In some embodiments, ligand L A It can be In some of the above embodiments, X 1 To X 6 Each of them can be C independently. In some of the above embodiments, X 1 To X 6 One of them can be N. In some of the above embodiments, X 1 To X 3 One of them can be N. In some of the above embodiments, X 3 To X 6 One of them can be N. In some of the above embodiments, R A1 R A2 R A3 and R C One of them can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R A1 One of them can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R A2 One of them can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R A3 One of them can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R C One of them can be alkyl, cycloalkyl, fluorine, deuterium, aryl, heteroaryl, or a combination thereof. In some of the above embodiments, R A1 R A2and R A3 One of them can be tert-butyl or phenyl. In some of the above embodiments, R A1 One of them can be tert-butyl or a substituted or unsubstituted phenyl group. In some of the above embodiments, R... A2 One of them can be tert-butyl, or a substituted or unsubstituted phenyl group. In some of the above embodiments, R A3 One of them can be tert-butyl, or a substituted or unsubstituted phenyl group. In some of the above embodiments, R C One of them can be tert-butyl, or a substituted or unsubstituted phenyl group. In some of the above embodiments, R... A1 One of them is a phenyl group that can be completely deuterated. In some of the above embodiments, R A2 One of them can be a fully deuterated phenyl group. In some of the above embodiments, R A3 One of them is a phenyl group that can be completely deuterated. In some of the above embodiments, each R A1 Independently, it is deuterium. In some of the above embodiments, each R A2 Independently, it is deuterium. In some of the above embodiments, each R A3 Independently, it is deuterium. In some of the above embodiments, each R C Deuterium is independent. In some of the above embodiments, R A1 R A2 R A3 and R C Each is deuterium, independently. In some of the above embodiments, R A1 R A2 R A3 and R C Each is H independently. In some of the above embodiments, the two Rs B They can be connected to form 5- or 6-membered aromatic rings. In some of the above embodiments, an R C With an R B They can be connected to form a ring.

[0090] In some embodiments, ligand L A You can choose from the following groups: L A 1-(R s (R) t (R) u L A 2-(R s (R) t (R) u L A 3-(R s (R) t (R) u L A 4-(R s (R) t)(R u )、L A 5-(R s )(R t )(R u )、L A 6-(R s )(R t )(R u )、L A 7-(R s )(R t )(R u )、L A 8-(R s )(R t )(R u )、L A 9-(R s )(R t )(R u )、L A 10-(R s )(R t )(R u )、L A 11-(R s )(R t )(R u )、L A 12-(R s )(R t )(R u )、L A 13-(R s )(R t )(R u )、L A 14-(R s )(R t )(R u )、L A 15-(R s )(R t )(R u )、L A 16-(R s )(R t )(R u )、L A 17-(R s )(R t )(R u )、L A 18-(R s )(R t )(R u )、L A 19-(R s )(R t )(R uL A 20-(R s (R) t (R) u L A 21-(R s (R) t (R) u L A 22-(R s (R) t (R) u L A 23-(R s (R) t (R) u L A 24-(R s (R) t (R) u L A 25-(R s (R) t (R) u L A 26-(R s (R) t (R) u L A 27-(R s (R) t (R) u L A 28-(R s (R) t (R) u L A 29-(R s (R) t (R) u L A 30-(R s (R) t (R) u L A 31-(R s (R) t (R) u ) and L A 32-(R s (R) t (R) u ),in s , t and u Each is an independent integer from 1 to 87, where:

[0091]

[0092]

[0093]

[0094]

[0095] R1 to R87 have the following structures:

[0096] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0097] In some embodiments, the compound may have the formula M(L) A ) p (L B ) q (L C ) r L B and L C Each is a bidentate ligand; and p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of metal M.

[0098] In some embodiments, the compound may have the formula selected from the group consisting of: Ir(L A 3. Ir(L) A (L) B )2、Ir(L A )2(L B ), Ir(L A )2(L C ) and Ir(L A (L) B (L) C ); and L A L B and L C They are different from each other.

[0099] In some embodiments, the compound may have the formula Pt(L) A (L) B ); and L A With L B They can be the same or different. In some embodiments, L A With LB They connect to form tetradentate ligands.

[0100] In some embodiments, L B and L C Each can independently choose from the following groups:

[0101] , , , , , , , , , , , , , , , , , , ,

[0102] , , and ,

[0103] in:

[0104] T is chosen from the group consisting of B, Al, Ga, and In;

[0105] Y 1 To Y 13 Each group is independently selected from the groups composed of carbon and nitrogen;

[0106] Y' selects from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f ;

[0107] R e and R f They can be fused or joined to form rings;

[0108] Each R a R b R c and R dIndependently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops;

[0109] R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; general substituents as defined herein; and

[0110] Any two adjacent R a R b R c R d R e and R f They can fused or connected to form rings or form polydentate ligands.

[0111] In some embodiments, L B and L C Each can independently choose from the following groups:

[0112] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

[0113] , , , , ,

[0114] and ,

[0115] in:

[0116] R a '、R b 'and R c 'Independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops;

[0117] R a1 R b1 R c1 R a R b R c R N R a '、R b 'and R c Each of these substituents is independently hydrogen or selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and

[0118] Any two adjacent R a '、R b 'and R c They can fused or connected to form rings or form polydentate ligands.

[0119] In some embodiments, the compound may be selected from the group consisting of: Ir(L A )3, Ir(L A (L) Bk )2、Ir(L A (L) BBn)2、Ir(L A )2(L Bk ), Ir(L A )2(L BBn ), Ir(L A )2(L Cj-I ) and Ir(L A )2(L Cj-II ),

[0120] Where L A It is a ligand as defined in this article;

[0121] in k It is an integer from 1 to 324, and each L Bk The following definitions are provided in Listing 2:

[0122] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

[0123] 、 、 、 , , ,

[0124] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0125] in n It is an integer from 1 to 180, and each L BBn The following definitions are provided in Listing 3:

[0126] 、 、 、 、 、 、 、

[0127] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0128] Each L Cj-I It has a structure based on the following formula: ;and

[0129] Each L Cj-II It has a structure based on the following formula: For L Cj-I and L Cj-II Each L in Cj As far as R is concerned, 201 and R 202 Each is defined independently as shown in Listing 4 below:

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] Where R D1 To R D246 It has the following structure:

[0141] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

[0142] , , , , and .

[0143] In some embodiments, the compound may have the formula Ir(L A (L) Bk )2、Ir(L A (L) BBn )2、Ir(L A )2(L Bk ) or Ir(L A )2(L BBn ), wherein the compound is composed of L Bk or L BBn Only one of the following components of the ligand: L B1 LB2 and L B18 and L B28 and L B38 and L B108 and L B118 and L B122 and L B124 and L B126 and L B128 and L B130 and L B132 and L B134 and L B136 and L B138 and L B140 and L B142 and L B144 [[ID=3)5]] and L B156 and L B158 and L B160 and L B162 and L B164 and L B168 and L B172 and L B175 and L B204 and L B206 and L B214 and L B216 and L B218 and L B220 and L B222 and L B231 and L B233 and L B235 and L B237 and L B240 and L B242 and L B244 and L B246 and L B248 and L B250 and L B252 and L B254 and L B256 and L B258 and L B260 and L B262 and L B264 and L B265 and L B266 and L B267 and L B268 and L B269 and L B270 and L BB1 and L<0……0338> and L BB3 and L BB4 and L BB5 and L BB6 and L BB7 and L BB8 and L BB9 and L BB10 and L BB11L BB2 L BB13 L BB14 L BB15 L BB16 L BB17 L BB18 L BB20 L BB22 L BB24 L BB34 L BB37 L BB71 L BB74 L BB88 L BB90 L BB97 L BB103 L BB104 L BB105 L BB106 L BB107 L BB112 L BB113 L BB115 L BB116 L BB117 L BB118 L BB119 L BB121 L BB122 and L BB123 .

[0144] In some embodiments, the compound may have the formula Ir(L A (L) Bk )2、Ir(L A (L) BBn )2、Ir(L A )2(L Bk ) or Ir(L A )2(L BBn ), wherein the compound is composed of L Bk or L BBn Only one of the following components of the ligand: L B1 L B2 L B18 L B28 L B38 L B108 L B118 L B122 L B126 L B128 L B132 L B136 L B138 L B142 L B156 L B162 L B204 L B206 L B214L B216 L B218 L B220 L B231 L B233 L B237 L B264 L B265 L B266 L B267 L B268 L B269 L B270 L BB1 L BB2 L BB3 L BB4 L BB5 L BB6 L BB13 L BB14 L BB18 L BB20 L BB22 L BB24 L BB34 L BB37 L BB103 L BB104 L BB107 L BB113 L BB115 L BB116 and L BB121 .

[0145] In some embodiments, the compound may have the formula Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ), where for L Cj-I and L Cj-II Specifically, the compound contains only its corresponding R 201 and R 202 Those L defined as one of the following structures Cj-I and L Cj-II Ligand: R D1 R D3 R D4 R D5 R D9 R D10 R D17 R D18 R D20 R D22 R D37 R D40 R D41 R D42 R D43 R D48 R D49 RD50 R D54 R D55 R D58 R D59 R D78 R D79 R D81 R D87 R D88 R D89 R D93 R D116 R D117 R D118 R D119 R D120 R D133 R D134 R D135 R D136 R D143 R D144 R D145 R D146 R D147 R D149 R D151 R D154 R D155 R D161 R D175 R D190 R D193 R D200 R D201 R D206 R D210 R D214 R D215 R D216 R D218 R D219 R D220 R D227 R D237 R D241 R D242 R D245 and R D246 .

[0146] In some embodiments, the compound may have the formula Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ), where for L Cj-I and L Cj-II Specifically, the compound contains only its corresponding R 201 and R 202 Those L defined as one of the following structures Cj-I and L Cj-II Ligand: R D1 RD3 R D4 R D5 R D9 R D10 R D17 R D22 R D43 R D50 R D78 R D116 R D118 R D133 R D134 R D135 R D136 R D143 R D144 R D145 R D146 R D149 R D151 R D154 R D155 R D190 R D193 R D200 R D201 R D206 R D210 R D214 R D215 R D216 R D218 R D219 R D220 R D227 R D237 R D241 R D242 R D245 and R D246 .

[0147] In some embodiments, the compound may have the formula Ir(L A )2(L Cj-I ), and the compound is composed of L Cj-I Only one of the following components of a ligand:

[0148] , , , , ,

[0149] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0150] In some embodiments, the compound may be selected from the group consisting of:

[0151] , , , , , and

[0152] .

[0153] In some embodiments, the compound may have the following structure

[0154] Formula III ,or

[0155] Formula IV ,

[0156] in:

[0157] M 1 It is either Pd or Pt;

[0158] Parts C and D are each independently monocyclic or polycyclic ring structures containing 5-membered and / or 6-membered carbon rings or heterocycles;

[0159] Z 1 and Z 2 Each can be either C or N independently;

[0160] K 1 K 2 and K 3 Each independently selects a group consisting of direct keys, O, and S, where K1 K 2 or K 3 At least two of them are direct bonds;

[0161] L 1 L 2 and L 3 Each is independently selected from the following groups: direct bond, BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO2, C=CRR', CRR', SiRR', GeRR', alkyl, cycloalkyl and combinations thereof, wherein L is present. 1 and L 2 At least one of them;

[0162] n1, n2, and n3 are each 0 or 1, and n1 + n2 + n3 = 2 or 3;

[0163] X 7 To X 9 Each can be either C or N independently;

[0164] R C and R D Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops;

[0165] R C and R D Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof;

[0166] Where chemically feasible, any two adjacent R A R B R C R D or R 1 They can be connected or fused together to form a ring; and

[0167] X 1 To X 6 R A R B Both ring A and ring A are the same as previously defined.

[0168] In some embodiments, both portion C and portion D can be a 6-membered aromatic ring. In some embodiments, portion C can be a 5-membered or 6-membered heteroaromatic ring.

[0169] In some embodiments, Z 2 It is N and Z 1 It is C. In some embodiments, Z 2It can be C and Z 1 It can be N.

[0170] In some embodiments, L 1 It can be O, SiRR', or CRR'. In some embodiments, L 2 It can be a direct key. In some embodiments, L 2 It can be NR.

[0171] In some embodiments, K 1 K 2 and K 3 Each can be a direct key. In some embodiments, K 1 K 2 or K 3 One of them can be O. In some embodiments, K 1 or K 2 One of them can be O. In some embodiments, K 3 It can be O.

[0172] In some embodiments, X 7 To X 9 All can be C.

[0173] In some embodiments, the compound may have the following structure

[0174] Formula V , or VI ,

[0175] Z 3 It is C or N; the remaining variables are the same as previously defined; and any two adjacent R A R B R C R D or R 1 They can be connected or fused together to form a ring.

[0176] In some embodiments of formula V or formula VI, R1, R A and R B Each can be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0177] In some embodiments, X 1 To X 3 Each can be C. In some embodiments, X 4 To X 6 Each can be C. In some embodiments, X 1 To X 6Each of them is C.

[0178] In some embodiments, two adjacent R A Substituents can connect to form a ring fused with ring A. In some embodiments, when ring A is a 7-membered, 8-membered, 9-membered, or 10-membered ring, the other two adjacent R groups... A Substituents can connect to form another ring fused with ring A. In some embodiments, a total of 6 adjacent Rs are present. A Substituents can be linked to form three separate rings, each fused to ring A. In some embodiments, all fused rings can be 5- or 6-membered aromatic rings. In some embodiments, each fused ring can be independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, each fused ring can be benzene.

[0179] In some embodiments, one R1 substituent of formula V is combined with one R B Substituents can connect to form a ring. In some embodiments, one R1 substituent in Formula V is linked to one R... A Substituents can connect to form a ring. In some embodiments, one R in Formula VI... C Substituents with an R B Substituents can connect to form a ring. In some embodiments, one R in Formula VI... C Substituents with an R A Substituents can connect to form a ring. In some embodiments, two adjacent R groups... B Substituents can connect to form a fused ring. In some embodiments, two adjacent R... C Substituents can connect to form fused rings.

[0180] In some embodiments, ring C and ring D may each be independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole.

[0181] In some embodiments, the compound may be selected from the group consisting of the structures listed in Listing 5 below:

[0182] , ,

[0183] , , , ,

[0184] , ,

[0185] , ,

[0186] , ,

[0187] , , , , , ,

[0188] , ,

[0189] and , where: R x and R y Each is selected from the following groups: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R G Each time it appears, it is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and X 1 To X 6 R1, R A R B R C R E R F L 1 The definitions of ring A and ring A are the same as those above.

[0190] In some embodiments, the compound may have the following structure

[0191] Formula V: ,or

[0192] Formula VI: L A' Choose from the following groups: L A' 1-(R s (R) t (R) u L A' 2-(R s (R) t (R) u L A' 3-(R s (R) t (R) u L A' 4-(Rs (R) t (R) u L A' 5-(R s (R) t (R) u L A' 6-(R s (R) t (R) u L A' 7-(R s (R) t (R) u L A' 8-(R s (R) t (R) u ) and L A' 9-(R s (R) t (R) u ),in s , t and u Each is an independent integer from 1 to 87, where:

[0193]

[0194] Where L A" Choose from the following groups: L A" 1-(R s (R) t (R) u L A" 2-(R s (R) t (R) u L A" 3-(R s (R) t (R) u L A" 4-(R s (R) t (R) u L A" 5-(R s (R) t (R) u L A" 6-(R s (R) t (R) u L A" 7-(R s (R) t (R) u L A" 8-(Rs )(R t )(R u )、L A" 9-(R s )(R t )(R u )、L A" 10-(R s )(R t )(R u )、L A" 11-(R s )(R t )(R u )、L A" 12-(R s )(R t )(R u )、L A" 13-(R s )(R t )(R u )、L A" 14-(R s )(R t )(R u )、L A" 15-(R s )(R t )(R u )、L A" 16-(R s )(R t )(R u )、L A" 17-(R s )(R t )(R u )、L A" 18-(R s )(R t )(R u )、L A" 19-(R s )(R t )(R u )、L A" 20-(R s )(R t )(R u )、L A" 21-(R s )(R t )(R u )、L A" 22-(R s )(R t )(R u )、L A" 23-(R s(R) t (R) u ) and L A" 24-(R s (R) t (R) u ),in s , t and u Each is an independent integer from 1 to 87, where:

[0195]

[0196]

[0197]

[0198] Among them, ligand L Y You can choose from the following groups: L Y 1-(R s (R) t (R) u L Y 2-(R s (R) t (R) u L Y 3-(R s (R) t (R) u L Y 4-(R s (R) t (R) u L Y 5-(R s (R) t (R) u L Y 6-(R s (R) t (R) u L Y 7-(R s (R) t (R) u L Y 8-(R s (R) t (R) u L Y 9-(R s (R) t (R) u L Y 10-(R s (R) t (R) u L Y11-(R s )(R t )(R u )、L Y 12-(R s )(R t )(R u )、L Y 13-(R s )(R t )(R u )、L Y 14-(R s )(R t )(R u )、L Y 15-(R s )(R t )(R u )、L Y 16-(R s )(R t )(R u )、L Y 17-(R s )(R t )(R u )、L Y 18-(R s )(R t )(R u )、L Y 19-(R s )(R t )(R u )、L Y 20-(R s )(R t )(R u )、L Y 21-(R s )(R t )(R u )、L Y 22-(R s )(R t )(R u )、L Y 23-(R s )(R t )(R u )、L Y 24-(R s )(R t )(R u )、L Y 25-(R s )(R t )(R u )、L Y 26-(Rs (R) t (R) u L Y 27-(R s (R) t (R) u L Y 28-(R s (R) t (R) u L Y 29-(R s (R) t (R) u L Y 30-(R s (R) t (R) u L Y 31-(R s (R) t (R) u L Y 32-(R s (R) t (R) u L Y 33-(R s (R) t (R) u ),in s , t and u Each is an independent integer from 1 to 87, where:

[0199]

[0200]

[0201]

[0202]

[0203] R1 to R87 have the following structures:

[0204] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0205] In some embodiments, the compound may be selected from the group consisting of the structures listed in Listing 9 below:

[0206] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , and .

[0207] In some embodiments, the compound may be selected from the group consisting of the following structures:

[0208] , , ,

[0209] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and

[0210] .

[0211] In some embodiments, ligands of formula I or II as described herein are included. AThe compound may be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its general meaning and includes the percentage of possible hydrogen atoms replaced by deuterium atoms (e.g., the positions of hydrogen or deuterium).

[0212] In some embodiments, ligands of formula I or formula II as described herein are used. A The compound may be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its general meaning and includes the percentage of possible hydrogen atoms replaced by deuterium atoms (e.g., the positions of hydrogen, deuterium, or halogen).

[0213] C. OLEDs and devices disclosed herein

[0214] In another aspect, this disclosure also provides an OLED device comprising an organic layer containing compounds as disclosed in the above-described compound section of this disclosure.

[0215] In some embodiments, the organic layer may contain ligands of the following formula: L A compounds

[0216] Formula I , or Formula II ,

[0217] Among them, ring A is an independent 5- to 10-membered heterocyclic ring; X 1 To X 6 Each is independently C or N; K 3 It is a direct bond, O or S; the maximum number of N atoms connected to each other within the ring is two; R A R B and R C Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein, wherein the ligand L A It complexes with metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and any two adjacent R A RB R C or R 1 The compounds may connect or fuse to form rings, provided that the compounds do not contain any of the structures shown below:

[0218] or .

[0219] In some embodiments, the organic layer may be an emission layer and the compound as described herein may be an emission dopant or a non-emission dopant.

[0220] In some embodiments, the organic layer may further comprise a body comprising a benzofused thiophene or a benzofused furan containing triphenylene, wherein any substituent in the body 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, where n is 1 to 10; and where Ar1 and Ar2 are independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole and their heteroaromatic analogs.

[0221] In some embodiments, the organic layer may further comprise a body comprising at least one chemical moiety selected from the group consisting of: naphthalene, fluorene, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5,9-dioxa-13b-boronnaphthalene[3,2,1-de]anthracene, aza-fluorene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenene, and aza-(5,9-dioxa-13b-boronnaphthalene[3,2,1-de]anthracene).

[0222] In some embodiments, the subject may be selected from the following group:

[0223] , , , , , , , , , , , , , , , , , , , , , , , ,

[0224] , , ,

[0225] , , , ,

[0226] , And its combination.

[0227] In some embodiments, the organic layer may further comprise a body, wherein the body comprises a metal complex.

[0228] In some embodiments, the compound as described herein may be a sensitizer; the device may further include a receptor; and the receptor may be selected from the group consisting of fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

[0229] In another aspect, the OLED of this disclosure may also include an emission region containing compounds as disclosed in the compound section of this disclosure above.

[0230] In some embodiments, the emission region may include a ligand L of the following formula. A compounds

[0231] Formula I , or Formula II ,

[0232] Among them, ring A is an independent 5- to 10-membered heterocyclic ring; X 1 To X 6 Each is independently C or N; K 3 It is a direct bond, O or S; the maximum number of N atoms connected to each other within the ring is two; R A R B and R CEach independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein, wherein the ligand L A It complexes with metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and any two adjacent R A R B R C or R 1 The compounds may connect or fuse to form rings, provided that the compounds do not contain any of the structures shown below:

[0233] or .

[0234] In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emitter layer serves as a reinforcement layer. The reinforcement layer comprises a plasmonic material exhibiting surface plasmon resonance, which is nonradiatively coupled to the emitter material and transfers excited-state energy from the emitter material to the nonradiative mode of the surface plasmon polaritons. The reinforcement layer is positioned at a distance from the organic emitter layer not exceeding a threshold distance, wherein, due to the presence of the reinforcement layer, the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total nonradiative decay rate constant equals the total radiative decay rate constant. In some embodiments, the OLED further comprises an external coupling layer. In some embodiments, the external coupling layer is disposed on the reinforcement layer on the opposite side of the organic emitter layer. In some embodiments, the external coupling layer is disposed on the emitter layer on the side opposite to the reinforcement layer, but still externally couples energy from the surface plasmon polaritons of the reinforcement layer. The external coupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, energy is scattered from the surface plasmon modes of the device into other modes, such as, but not limited to, organic waveguide modes, substrate modes, or another waveguide mode. If energy is scattered into the non-free-space modes of the OLED, other external coupling schemes can be combined to extract the energy into free space. In some embodiments, one or more intermediary layers may be disposed between the enhancement layer and the external coupling layer. Examples of intermediary layers may be dielectric materials, including organic, inorganic, perovskite, and oxide materials, and may include stacks and / or mixtures of these materials.

[0235] The enhancement layer improves the effective properties of the medium in which the emitter material resides, thereby causing any or all of the following: reduced emissivity, modified emission profile, emission intensity variation with angle, altered emitter material stability, altered OLED efficiency, and reduced efficiency roll-off of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides produces an OLED device that utilizes any of the above effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLED according to this disclosure may also include any other functional layers commonly found in OLEDs.

[0236] The reinforcing layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Typically, metamaterials are media composed of different materials, wherein the effect of the medium as a whole differs from the sum of its material components. Specifically, we define an optically active metamaterial as a material that simultaneously possesses negative permittivity and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs for different spatial orientations. Optically active metamaterials and hyperbolic metamaterials differ significantly from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the medium should exhibit uniformity along the propagation direction on a length scale of the light wavelength. Using terminology understandable to those skilled in the art, the dielectric constant of the metamaterial along the propagation direction can be described by an effective dielectric approximation. Plasmon materials and metamaterials offer methods for controlling light propagation, which can enhance OLED performance in a variety of ways.

[0237] In some embodiments, the enhancement layer is configured as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features arranged periodically, quasi-periodicly, or randomly, or subwavelength-sized features arranged periodically, quasi-periodicly, or randomly. In some embodiments, the wavelength-sized features and subwavelength-sized features have sharp edges.

[0238] In some embodiments, the outer coupling layer is characterized by a wavelength size arranged periodically, quasi-periodicly, or randomly, or by a subwavelength size arranged periodically, quasi-periodicly, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outer coupling can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and / or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layering of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles may have additional layers disposed on them. In some embodiments, the outer coupling layer can be used to tune the polarization of the emission. Changing the size and periodicity of the outer coupling layer can select the polarization type preferentially coupled to air. In some embodiments, the outer coupling layer also functions as an electrode of the device.

[0239] In another aspect, this disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise compounds as disclosed in the above compound section of this disclosure.

[0240] In some embodiments, a consumer product includes 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 of the following formula: A compounds

[0241] Formula I , or Formula II ,

[0242] Among them, ring A is an independent 5- to 10-membered heterocyclic ring; X 1 To X 6 Each is independently C or N; K 3 It is a direct bond, O or S; the maximum number of N atoms connected to each other within the ring is two; R A R Band R C Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein, wherein the ligand L A It complexes with metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and any two adjacent R A R B R C or R 1 The compounds may connect or fuse to form rings, provided that the compounds do not contain any of the structures shown below:

[0243] or .

[0244] In some embodiments, a consumer product may be one of the following: a flat panel display, a computer monitor, a medical monitor, a television set, a signboard, a light for internal or external lighting and / or signaling, a head-up display, a fully transparent 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 with a diagonal of less than 2 inches, a 3D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a phototherapy device, and a sign.

[0245] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. 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 photoemission mechanism, light is emitted. In some cases, excitons may be localized on excimers or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0246] Certain OLED materials and configurations are described in U.S. Patents 5,844,363, 6,303,238 and 5,707,745, which are incorporated herein by reference in their entirety.

[0247] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs within timeframes of less than 10 nanoseconds.

[0248] Recently, OLEDs with emitting materials that emit light from the triplet state (“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,” Applied Physics Letters, Vol. 75, 3, 4-6 (1999) (“Baldo-II”), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0249] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. 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. Device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0250] Further examples of each of these layers are available. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein 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 herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses 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 herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0251] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below the anode 230, the 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 the device 200. Figure 2 Provide an example of how some layers can be omitted from the structure of device 100.

[0252] Figure 1 and 2The simple layered structures described herein are provided by way of non-limiting examples, and it should be understood that embodiments of this disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can be used. Furthermore, 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 emitter layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of the different organic materials mentioned above.

[0253] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example as described in, for example, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can deviate from... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0254] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include patterning via mask deposition, cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and some of the methods associated with deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handleability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0255] The device manufactured according to embodiments of this disclosure may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in an environment including moisture, vapor, and / or gases. The barrier layer may be deposited on, under, or adjacent to a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using a variety of known chemical vapor deposition techniques and may comprise compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may contain inorganic or organic compounds, or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For the process to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited and / or deposited simultaneously under the same reaction conditions. The weight ratio of polymeric to non-polymeric materials can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0256] The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes compounds of this disclosure in its organic layer. The consumer product should include any type of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, phototherapy devices, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to this disclosure. Many of the devices are intended for use in temperature ranges 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).

[0257] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0258] 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 utilize the materials and structures described herein. More generally, organic devices such as organic transistors can utilize the materials and structures described herein.

[0259] 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 including carbon nanotubes.

[0260] In some embodiments, the OLED further comprises a layer including a delayed phosphor emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. 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 with 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 with a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0261] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known 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 annihilation, or a combination of these processes. In some embodiments, the emission dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compound may be homogeneous (each ligand is identical). In some embodiments, the compound may be mixed (at least one ligand is different from the others). In some embodiments, when more than one ligand coordinated to a metal is present, the ligands may all be identical. In some other embodiments, at least one ligand is different from the others. In some embodiments, each ligand may be different from each other. This also applies in embodiments where a ligand coordinated to a metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Therefore, in the case where the coordinating ligands are linked together, in some embodiments all the ligands may be the same, and in some other embodiments at least one of the linking ligands may be different from (multiple) other ligands.

[0262] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain acceptors in the form of one or more fluorescent and / or delayed-motion fluorescent emitters. In some embodiments, the compound can be used as a component of an excited-state 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 to emit energy or further transfer energy to the final emitter. The acceptor concentration can range from 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, emission can be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0263] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0264] The OLEDs disclosed herein can be incorporated into one or more consumer products, electronic component modules, and lighting panels. The organic layer can be an emission layer, and the compound can be an emission dopant in some embodiments, while in other embodiments it can be a non-emission dopant.

[0265] In another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components selected from the group consisting of: solvents, a host, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials.

[0266] This disclosure covers any chemical structure comprising the novel compounds of this disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but in which one hydrogen has been removed and replaced by a bond to the remainder of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but in which more than one hydrogen has been removed and replaced by one or more bonds to the remainder of the chemical structure. In the case of supramolecular compounds, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

[0267] D. Combinations of the compounds disclosed herein with other materials

[0268] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the emission dopants disclosed herein can be used in combination with a wide variety of host layers, transport layers, blocking layers, injection layers, electrodes, and other possible layers. 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 readily consult the literature to identify other materials that can be used in combination.

[0269] a) Conductive dopants:

[0270] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by creating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0271] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein in OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.

[0272] , , ,

[0273] , ,

[0274] , , , ,

[0275] , , and .

[0276] b) HIL / HTL:

[0277] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used, provided that the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0278] Examples of HIL / HTL can be found in paragraphs

[0111] through

[0117] of U.S. Application Publication No. US2020 / 0,295,281A1 of Universal Display Corporation, the contents of which, along with the entire disclosure, are incorporated herein by reference in their entirety.

[0279] c) EBL:

[0280] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0281] d) Main body:

[0282] The light-emitting layer of the organic EL device disclosed herein preferably contains at least a metal complex as the light-emitting material, and may contain a host material using a metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used, as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material can be used with any dopant, as long as the triplet criterion is satisfied.

[0283] The main examples can be found in paragraphs

[0119] to

[0125] of U.S. Application Publication No. US2020 / 0,295,281A1 of General Display Corporation, and the contents of these paragraphs and the entire disclosure are incorporated herein by reference in their entirety.

[0284] e) Other emitters:

[0285] One or more other emitter dopants may be used in conjunction 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.

[0286] Non-limiting examples of emitter materials that can be combined with the materials disclosed herein for use in OLEDs are illustrated in paragraphs

[0126] to

[0127] of U.S. Application Publication No. US2020 / 0,295,281A1 of General Display Corporation, the contents of which and the entire disclosure are incorporated herein by reference in their entirety.

[0287] f) HBL:

[0288] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0289] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as those used in the main body described above.

[0290] In another aspect, the compounds used in HBL contain at least one of the following groups in their molecules:

[0291]

[0292] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0293] g) ETL:

[0294] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, provided it is typically used for electron transport.

[0295] In one aspect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0296]

[0297]

[0298] Where R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, which, when aryl or heteroaryl, have a similar definition to Ar as described above. 1 To Ar 3 It has a similar definition to Ar mentioned above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0299] In another aspect, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0300]

[0301] Wherein (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N or N, N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to the metal.

[0302] Non-limiting examples of emitter materials that can be combined with the materials disclosed herein for use in OLEDs are illustrated in paragraphs

[0131] through

[0134] of U.S. Application Publication No. US2020 / 0,295,281A1 of General Display Corporation, the contents of which and the entire disclosure are incorporated herein by reference in their entirety.

[0303] h) Charge Generation Layer (CGL)

[0304] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0305] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms may be partially or fully deuterated. The minimum amount of hydrogen in a deuterated compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Therefore, any specifically listed substituent, such as (but not limited to) methyl, phenyl, pyridyl, etc., can be in its undeuterated, partially deuterated, and fully deuterated form. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0306] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

[0307] Experimental Chapter

[0308] Synthesis of Launcher 1

[0309] Synthesis of 2-(2-((2-nitrophenyl)amino)phenyl)prop-2-ol

[0310]

[0311] 1-Iodo-2-nitrobenzene (3.75 g, 15.1 mmol), 2-(2-aminophenyl)prop-2-ol (2.28 g, 15.1 mmol), cesium carbonate (7.37 g, 22.6 mmol), Pd2dba3 (0.28 g, 0.30 mmol), and SPhos (0.49 g, 1.2 mmol) were added to a flask containing toluene (120 mL) and refluxed overnight. The reaction mixture was cooled to room temperature (RT) and filtered through diatomaceous earth. The residue was purified by column chromatography (10–20% ethyl acetate / heptane) to give the desired product (95% yield) as an orange solid.

[0312] Synthesis of 9,9-dimethyl-4-nitro-9,10-dihydroacridine

[0313]

[0314] 2-(2-((2-nitrophenyl)amino)phenyl)prop-2-ol (2.0 g, 7.3 mmol) and phosphoric acid (0.72 g, 7.34 mmol) were added to a flask and heated to 50 °C for 12 hours. The reaction mixture was cooled and poured into ice water. The red solid (96% yield) was collected by filtration.

[0315] Synthesis of 9,9-dimethyl-9,10-dihydroacryl-4-amine

[0316]

[0317] 9,9-Dimethyl-4-nitro-9,10-dihydroacridine (8.0 g, 31.4 mmol) and palladium / carbon (2.0 g) were added to a flask containing ethyl acetate and stirred overnight. The reaction mixture was filtered and evaporated to give the desired compound (86% yield).

[0318] Synthesis of 6,6-dimethyl-6H-2l2,11l4-imidazo[5,4,3-de]acridine:

[0319]

[0320] 9,9-Dimethyl-9,10-dihydroacrylidine-4-amine (12.0 g, 53.5 mmol), triethoxymethane (7.93 g, 53.5 mmol), and p-toluenesulfonic acid (1.02 g, 5.35 mmol) were added to a flask equipped with a stir bar and stirred overnight at 80 °C. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed with an aqueous sodium bicarbonate solution. The organic layers were combined, dried, and evaporated, and the residue was purified by column chromatography (2% MeOH / DCM) to give an oil (89% yield).

[0321] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-6,6-dimethyl-2,6-dihydroimidazo[4,5,1-de]acridin-11-onium tetrafluoroborate

[0322]

[0323] 6,6-Dimethyl-6H-2l2,11l4-imidazo[5,4,3-de]acridine (156 mg, 0.666 mmol), (3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)(trimethylyl)iodonium tetrafluoroborate (531 mg, 0.732 mmol), and bis(((trifluoromethyl)sulfonyl)oxy)copper (24.08 mg, 0.067 mmol) were added to a 25 mL test tube equipped with a stir bar and circulated in the tubing. Anhydrous DMF (6.658 mL) was added and the reaction mixture was heated to 120 °C overnight. The reaction mixture was cooled to room temperature and water was added to give a white precipitate. The aqueous layer was extracted three times with ethyl acetate. The organic layers were combined, washed with saturated LiCl solution, dried over MgSO4, filtered, and vacuum-sealed. Separation was performed by column chromatography using 1:1 CH3CN:DCM as the eluent. The pure eluates were combined and evaporated to give the desired compound as a white solid (55% yield).

[0324] Synthesis of Launcher 1

[0325]

[0326] 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-6,6-dimethyl-2,6-dihydroimidazo[4,5,1-de]acridin-11-onium tetrafluoroborate (194 mg, 0.272 mmol) was added to a 25 mL flask equipped with a stir bar. o-Dichlorobenzene (5 mL) was added via syringe, followed by potassium bis(trimethylsilyl)amino (0.272 mL, 0.272 mmol). Solid (COD)PtCl2 (102 mg, 0.272 mmol) was added, and the reaction mixture was heated to reflux. Thin-layer chromatography (TLC) using 1:1 Hep:DCM showed emission spots at approximately rf 0.5. A color gradient was observed from the top to the bottom of the spots. The reaction mixture was heated overnight. The reaction mixture was cooled to room temperature, and the solvent was removed by evaporation. The residue was purified by column chromatography to give the desired compound as a yellow solid (22% yield).

[0327] Synthesis of Launcher 2

[0328] Synthesis of 5-iodo-1-phenyl-1H-imidazolium

[0329]

[0330] Cu(OTf)₂ (3.15 g, 8.66 mmol, 5 mol%), cesium carbonate (85 g, 260 mmol), and 1-methylbenzimidazole (4.60 g, 34.7 mmol, 20 mol%) were loaded into a dry 1000 mL reaction tube. Hexafluoroisopropanol (700 mL) was added, and the mixture was stirred at room temperature for 30 min, followed by the addition of (1H-imidazol-5-yl)(phenyl)-13-iodoalkyl acetate (57.5 g, 173 mmol, 1.0 equivalent). The tube was capped, and the mixture was heated to 55 °C and maintained for 26 h. The solvent was removed, and the product was eluted with a hexane:EtOAc mixture (100% hexane to 50% hexane / EtOAc) and separated by column chromatography to give the desired product (40% yield).

[0331] Synthesis of 2,2-dimethyl-1-(1-phenyl-1H-imidazol-5-yl)prop-1-one:

[0332]

[0333] 5-Iodo-1-phenyl-1H-imidazole (0.320 g, 1.185 mmol, 1.0 equivalent) and THF (4 mL) were added to a round-bottom flask. The solution was cooled to -78°C and maintained for 30 minutes. Isopropylmagnesium chloride (1.03 mL, 1.303 mmol, 1.1 equivalent) was added dropwise to the stirred mixture over 2 minutes, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was cooled to -78°C and pentanoyl chloride (0.290 mL, 2.37 mmol, 2.0 equivalent) was added dropwise over 2 minutes. The reaction mixture was allowed to be stirred overnight at 23°C. The reaction mixture was quenched with saturated NH4Cl, diluted with EtOAc, washed with saturated NaCl and deionized water, and dried over Na2SO4. The crude product was purified by column chromatography (50% ethyl acetate:hexane) to give the desired product (42% yield).

[0334] Synthesis of 3,3-dimethyl-2-(1-phenyl-1H-imidazol-5-yl)but-2-ol:

[0335]

[0336] Add 0.150 g (0.657 mmol, 1 equivalent) and 3 mL of THF to a round-bottom flask. Cool the mixture to -78 °C for 15 min with stirring. Add methyllithium (1.00 mL, 1.64 mmol, 2.5 equivalent) dropwise to the solution. Allow the reaction mixture to stir at -78 °C for 1 h, then raise the temperature to room temperature and maintain for 4 h. Quench the reaction mixture with saturated NH4Cl at 0 °C and dilute with EtOAc, washing with saturated NH4Cl, saturated brine, and deionized water. Purify the reaction mixture by column chromatography to give the desired product (65% EtOAc / hexane) in 78% yield.

[0337] Synthesis of 4,4,5,5-tetramethyl-4,5-dihydroimidazo[1,5-a]quinoline:

[0338]

[0339] 3,3-Dimethyl-2-(1-phenyl-1H-imidazol-5-yl)but-2-ol (0.100 g, 0.409 mmol, 1 equivalent) and DCM (6 mL) were added to a flask equipped with a stir bar. The mixture was stirred at 0 °C for 30 min, and then aluminum trichloride (0.546 g, 4.09 mmol, 10 equivalent) was added in a single batch. The reaction mixture was stirred at 0 °C for 1 h, and then heated to room temperature and maintained for 5 h. The reaction mixture was cooled to 0 °C and quenched with saturated Na₂CO₃, diluted with ethyl acetate, and washed with brine and deionized water. The reaction mixture was purified by column chromatography (60% ethyl acetate / hexane) to give the desired product (96% yield).

[0340] Synthesis of 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-10l4-imidazo[1,5-a]quinoline tetrafluoroborate

[0341]

[0342] 4,4,5,5-Tetramethyl-4,5-dihydroimidazo[1,5-a]quinoline (0.40 g, 1.75 mmol), (3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)(trimethylyl)iodonium tetrafluoroborate (1.4 g, 1.933 mmol), and bis(((trifluoromethyl)sulfonyl)oxy)copper (0.064 g, 0.176 mmol) were added to a Schlenk tube equipped with a stir bar. Anhydrous DMF (6.658 mL) was added, and the reaction mixture was heated to 120 °C overnight. The reaction mixture was cooled to room temperature, and the solvent was evaporated. The residue was dissolved in a minimal amount of DCM, and Et₂O was added to give a grayish-white solid, which was collected by filtration (97% yield).

[0343] Synthesis of Launcher 2

[0344]

[0345] 2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-2H-imidazo[1,5-a]quinoline-10-onium tetrafluoroborate (100 mg, 0.142 mmol) and silver(I)-silver(III) oxide (16.44 mg, 0.071 mmol) were added to a 100 mL round-bottom flask equipped with a stir bar. 1,2-dichloroethane (3 mL) was added, and the reaction mixture was stirred overnight at room temperature. The solvent was evaporated, yielding foam. This foam was then reacted with (COD)PtCl2 (53.1 mg, 0.142 mmol) in o-dichlorobenzene (3.00 mL) under reflux overnight. The solvent was evaporated, and the residue was coated onto diatomaceous earth. The product was purified by column chromatography (2:1 DCM:heptane) to give a yellow solid (33% yield).

[0346] Synthesis of Launcher 3

[0347] Synthesis of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane

[0348]

[0349] Under nitrogen atmosphere, 1-bromo-2-chlorobenzene and anhydrous tetrahydrofuran were added to a 2 L three-necked round-bottom flask and the mixture was cooled to -72 °C. n-BuLi was added, and the solution was allowed to warm to room temperature. The mixture was then cooled again to -72 °C. nBuLi was added, and the reaction mixture was stirred for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoborhexacyclopentane was added, and the solution was allowed to warm to room temperature while stirring overnight. The reaction mixture was diluted with an aqueous solution of diethyl ether and HCl, the aqueous phase was extracted, and the combined organic compounds were dried over MgSO4 and filtered. The residue was purified by column chromatography to give 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborhexacyclopentane (80% yield) as a clear yellow oil.

[0350] Synthesis of 2"-chloro-2-fluoro-3-nitro-1,1':2',1"-biphenyl

[0351]

[0352] A solution of 2-(2'-chloro-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane in dioxane and water was added to a 2 L three-necked round-bottom flask, and the mixture was bubbled under nitrogen for 2 hours. Then, 1-bromo-2-fluoro-3-nitrobenzene, K₂CO₃, and Pd(PPh₃)₄ were added together. The reaction mixture was stirred vigorously at 95 °C. After 24 hours, the reaction mixture was cooled to room temperature and diluted with EtOAc and brine. The aqueous phase was extracted with EtOAc. The combined organic matter was dried over MgSO₄, filtered, and concentrated under vacuum to give a dark oil (63%).

[0353] Synthesis of 2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine:

[0354]

[0355] THF and K3PO4 were added to a 2 L three-necked round-bottom flask equipped with a diaphragm and a stir bar. Then, 2"-chloro-2-fluoro-3-nitro-1,1':2',1"-biterphenyl, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline and SPhosPdG2 were added together. The reaction mixture was stirred vigorously at 60 °C. After 24 hours, the reaction mixture was cooled to room temperature and EtOAc was added. The aqueous phase was extracted with EtOAc, the combined organic matter was dried over MgSO4, filtered, and concentrated under vacuum to give a viscous black oil. This was dissolved in dichloromethane and loaded onto a large silica gel stopper to give 2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-bitetraphenyl]-2-amine as a brown solid (83%).

[0356] Synthesis of 8-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0357]

[0358] In a 2 L round-bottom flask equipped with a diaphragm and a stir bar, a solution of 2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine in DMSO was prepared and stirred under nitrogen. K2CO3 was added and the reaction mixture was stirred vigorously at 150-160 °C. After 9 hours, the reaction mixture was cooled to room temperature and poured into deionized water. The aqueous layer was extracted with EtOAc. The combined organic matter was washed with brine and dried over MgSO4. The reaction mixture was filtered and concentrated under vacuum to give 85% (8-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone as an orange-red solid.

[0359] Synthesis of 9H-tetrabenzo[b,d,f,h]azacyclononaten-8-amine

[0360]

[0361] A suspension of 8-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine in MeOH was prepared in a 2 L round-bottom flask equipped with a diaphragm and a stir bar. Pd / C and hydrazine hydrate were added under nitrogen atmosphere, and the mixture was vigorously stirred at 60–65 °C. After 3 hours, the mixture was cooled and filtered through a diatomaceous earth stencil. The filtrate was concentrated under vacuum to give a creamy suspension. This suspension was diluted with water, and the aqueous phase was extracted with dichloromethane. The combined organic matter was washed with water and brine and dried over MgSO4. The residue was filtered and concentrated under vacuum to give 84% (9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine) as a brown solid.

[0362] Synthesis of 1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraeno[1,2,3-cd]indene

[0363]

[0364] 9H-tetrabenzo[b,d,f,h]azacyclononaten-8-amine (1 g, 2.99 mmol) was dissolved in triethoxymethane (24.90 ml, 150 mmol), bubbled with argon for 5 minutes, and hydrogen chloride (0.295 ml, 3.59 mmol) (37% aqueous solution) was added in a single addition at room temperature. The reaction mixture was heated to 80 °C and maintained for 16 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was diluted with diethyl ether and stirred for 30 minutes. The solid was filtered off to give a white solid product (0.9 g, 89%).

[0365] 1-(4-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(tetrafluoro-15-boronyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2-iodo-1-onthium-2-oxide

[0366]

[0367] In a pressure tube, 1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraeno[1,2,3-cd]indene (0.85 g, 2.468 mmol) and 9-(4-(tert-butyl)pyridin-2-yl)-2-(4-(trimethylyl(tetrafluoro-15-boryl)-13-iodoalkyl)phenoxy)-9H-carbazole (2.324 g, 3.21 mmol) were mixed in DMF (6 mL) and bubbled with nitrogen for five minutes. Bis(((trifluoromethyl)sulfonyl)oxy)copper (0.045 g, 0.123 mmol) was added to the mixture and bubbled for three minutes. The tube was sealed and stirred at 110 °C for 1 hour. The reaction mixture was cooled to room temperature, diluted with DCM, and evaporated to dryness to give a brown oil. The material was purified by column chromatography to obtain the product (2.05 g, 95%).

[0368] Synthesis of Launcher 3

[0369]

[0370] 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(tetrafluoro-15boryl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraenoate[1,2,3-cd]indene-2-iodo-1-onthium-2-oxide (250 mg, 0.304 mmol), potassium tetrachloroplatinate (126 mg, 0.304 mmol), and 2,6-dimethylpyridine (130 mg, 1.215 mmol) were suspended in 1,2-dichlorobenzene (15 ml) and bubbled under nitrogen for five minutes in a round-bottom flask. The flask was equipped with a condenser, and the reaction mixture was stirred at 125°C under nitrogen for 24 hours. The reactants were cooled to room temperature and the product (0.1 g, 36%) was purified by column chromatography.

[0371] Synthesis of Launcher 4

[0372] Synthesis of 3-bromo-[1,1'-biphenyl]-2-amine:

[0373]

[0374] In a 2 L round-bottom flask, ethanol (300 mL) and water (300 mL) were added to a suspension of 2,6-dibromoaniline (30 g, 117 mmol), phenylboronic acid (14.43 g, 117 mmol), sodium carbonate (74.6 g, 703 mmol), and Pd(PPh3)4 (6.84 g, 5.86 mmol) in toluene (1.2 L). The flask was purged with nitrogen for 20 min, and the reaction mixture was stirred under reflux for 5 h. The reaction mixture was cooled to room temperature, water (750 mL) was added, and the two layers were separated. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography to give a white solid (86.31 g, 72%).

[0375] Synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborphane-2-yl)-[1,1'-biphenyl]-2-amine

[0376]

[0377] 3-Bromo-[1,1'-biphenyl]-2-amine (40 g, 156 mmol), potassium acetate (23.18 g, 234 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxoboronylcyclopentane) (84 g, 327 mmol), Pd(dppf)Cl2.CH2Cl2 (6.41 g, 7.79 mmol), and dimethyl sulfoxide (1 L) were introduced into a 2 L round-bottom flask, and the mixture was purged with nitrogen for 20 min, followed by heating at 80 °C for 3.5 h. The reaction mixture was cooled to room temperature, and a saturated aqueous solution of ammonium chloride and ethyl acetate were added to the reaction mixture. The two layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with 1 L NaCl solution, dried over MgSO4, filtered, and concentrated under vacuum to obtain an oily substance. The product (37.7 g, 77%) was purified by column chromatography to obtain a pale yellow solid.

[0378] Synthesis of 2-fluoro-3-nitro-[1,1':2',1":2",1"':3"',1""-pentaphenyl]-2"'-amine

[0379]

[0380] In a 2 L round-bottom flask, tetrahydrofuran (380 ml), tripotassium phosphate (573 ml, 287 mmol) (0.5 M aqueous solution), 2"-chloro-2-fluoro-3-nitro-1,1':2',1"-biphenyl (40 g, 110 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)-[1,1'-biphenyl]-2-amine (44.9 g, 144 mmol), and Sphos-Pd-G2 (4.12 g, 5.60 mmol) were added, and the reaction mixture was stirred overnight at 60 °C under nitrogen. The reaction mixture was cooled to room temperature. Ethyl acetate was added, the two layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated. The residue was purified by column chromatography to give a product as a yellow solid. This solid was suspended in heptane and stirred for 3 hours. The suspension was filtered and washed with heptane to give a product (47.85 g, 92%) as a yellow solid.

[0381] Synthesis of 8-nitro-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0382]

[0383] Potassium carbonate (18.25 g, 132 mmol) was added to a 2 L round-bottom flask containing 2-fluoro-3-nitro-[1,1':2',1":2",1"':3"',1""-pentaphenyl]-2""-amine (32 g, 66.0 mmol) in dimethyl sulfoxide (1000 ml), and the flask was purged with nitrogen for 30 min. The reaction mixture was then stirred overnight at 155 °C. The reaction mixture was cooled to room temperature, and cold saturated sodium chloride solution and ethyl acetate were added. The aqueous layer was extracted several times with ethyl acetate. The organic layers were combined and evacuated to give an oil, which was purified by column chromatography. The solid was suspended in heptane and stirred for two days. The suspension was filtered and the solid was washed twice with heptane to give a product (37.15 g, 64%) as an orange solid.

[0384] Synthesis of 10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0385]

[0386] Under N2 atmosphere, Pd / C (8.62 g, 8.10 mmol, 10 wt%) was added to a 2 L round-bottom flask containing a suspension of 8-nitro-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (36.5 g, 81 mmol) in methanol (1.25 L), followed by the addition of hydrazine hydrate (101 ml, 1619 mmol). The mixture was stirred vigorously at 70 °C (oil bath) under nitrogen atmosphere for 5 hours. The reaction mixture was cooled to room temperature and filtered through a diatomaceous earth stencil. It was washed with methanol (100 ml) and then with dichloromethane (4 × 250 ml). The product was purified by column chromatography to give a grayish-white solid (31.55 g, 94%).

[0387] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0388]

[0389] Sodium tert-butoxide (0.489 g, 5.09 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (0.697 g, 1.697 mmol), and 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (0.8 g, 1.697 mmol) were placed in a 250 mL round-bottom flask and purged with N2. Toluene (6.79 mL) and Sphos-Pd-G2 (0.066 g, 0.085 mmol) were then added, and the reaction mixture was stirred under reflux. The mixture was cooled to room temperature, filtered, and evacuated. The product (1.3 g, 88% yield) was purified by column chromatography.

[0390] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium bromide:

[0391]

[0392] N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (45.9 g, 57.3 mmol) was dissolved in refluxed triethoxymethane (95 mL, 573 mmol) and cooled to room temperature. Hydrogen bromide (7.08 mL, 63.0 mmol) was added and the mixture was stirred overnight at room temperature. The solvent was removed under vacuum and the substance was purified by column chromatography to give a product as a grayish-white solid (34.22 g, 63.6% yield).

[0393] Synthesis of Launcher 4

[0394]

[0395] In a 250 mL round-bottom flask, 1,3,5-trimethoxybenzene (0.489 g, 2.90 mmol), 2,6-dimethylpyridine (2.243 mL, 19.36 mmol), 2-bromo-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraenoate[1,2,3-cd]indene (15.7 g, 17.60 mmol), and Pt(acac)₂ (6.92 g, 17.60 mmol) were dissolved / suspended in propionic acid (37 mL, 17.60 mmol). The reaction mixture was heated at 150 °C overnight. The reactants were filtered, and the filtered solid was redissolved in DCM and dissolved in water. The organic layer was retained, concentrated, and separated by column chromatography to give a yellow solid (12.1 g, 67.6% yield).

[0396] Synthesis of Launcher 5

[0397] Synthesis of 4-bromo-2-(tert-butyl)aniline:

[0398]

[0399] In a 1 L round-bottom flask, 50 g (328 mmol) of 2-(tert-butyl)aniline was dissolved in 1.3 L of acetonitrile, and the flask was purged with nitrogen for 20 min. Ammonium acetate (2.61 g, 32.8 mmol) was then added, followed by ten fractions of 6.2 g each, with NBS (62.0 g, 345 mmol) added every ten minutes. A saturated aqueous solution of Na₂S₂O₃ (1.5 L) was added along with ethyl acetate, and the layers were separated. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO₄, filtered, and concentrated under vacuum. The residue was purified by column chromatography to give a red oily product (72.5 g, 97%).

[0400] Synthesis of 4-bromo-2-(tert-butyl)-6-chloroaniline

[0401]

[0402] 4-Bromo-2-(tert-butyl)aniline (63 g, 276 mmol) and DMF (1.05 l) were introduced into a 2 L round-bottom flask. The reaction mixture was purged with nitrogen for 20 min. Then, NCS (41.4 g, 304 mmol) was added in one go, and the flask was purged with nitrogen for 5 min. The reaction mixture was then stirred at 73 °C under nitrogen for 4 h. A saturated aqueous solution of Na₂S₂O₃ and ethyl acetate were added, and the layers were separated. The organic layer was washed with water, dried over MgSO₄, filtered, and concentrated under vacuum to give a red oily product (69.4 g, 94%).

[0403] Synthesis of 2-(tert-butyl)-6-chloroaniline

[0404]

[0405] 4-Bromo-2-(tert-butyl)-6-chloroaniline (20 g, 76 mmol), palladium / carbon (8.11 g, 7.62 mmol), and ethanol (160 mL) were introduced into a 350 mL pressure vessel. The reaction mixture was allowed to stand at 10 psi H₂ for 4 hours. The mixture was filtered through a diatomaceous earth mat and washed with ethanol. The filtrate was concentrated under vacuum. A saturated aqueous solution of sodium bicarbonate and ethyl acetate were added, and the layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO₄, filtered, and concentrated under vacuum to give an orange oily product (14.05 g, 81%).

[0406] Synthesis of 2-(tert-butyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline

[0407]

[0408] 2-(tert-butyl)-6-chloroaniline (25 g, 136 mmol) and 1,4-dioxane (550 mL) were introduced into a 2 L round-bottom flask, followed by Pd2dba3 (3.21 g, 3.40 mmol), dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (6.62 g, 13.61 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxoboronylcyclopentane) (105 g, 408 mmol), and potassium acetate (40.5 g, 408 mmol). The flask was purged with nitrogen for 20 min, and the reaction mixture was stirred under nitrogen and reflux for 4 h. After four h, the mixture was filtered through a diatomaceous earth filter and washed with ethyl acetate, and the filtrate was concentrated under vacuum. The product was purified by column chromatography to obtain an orange oily product (26.2 g, 63%).

[0409] Synthesis of 3-(tert-butyl)-2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine

[0410]

[0411] To a 500 mL round-bottom flask, tetrahydrofuran (63 mL), freshly prepared tripotassium phosphate aqueous solution (96 mL, 47.8 mmol) (0.5 M aqueous solution), 2"-chloro-2-fluoro-3-nitro-1,1':2',1"-bitriphenyl (6 g, 18.31 mmol), 2-(tert-butyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline (13.99 g, 45.8 mmol), and Sphos Pd G2 (0.673 g, 0.934 mmol) were introduced and the flask was purged with nitrogen for 30 min. The reaction mixture was then stirred vigorously at 60 °C under nitrogen for 20 h. The reaction mixture was then cooled to room temperature and ethyl acetate was added. The layers were separated, and the aqueous layer was further extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The product was purified by column chromatography to obtain a yellow solid (9.63 g, 78%).

[0412] Synthesis of 8-(tert-butyl)-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0413]

[0414] Cesium carbonate (23.45 g, 71.2 mmol) was added to a 1 L round-bottom flask containing a solution of 3-(tert-butyl)-2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine (11 g, 23.75 mmol) in anhydrous dimethyl sulfoxide (385 mL), and the flask was purged with nitrogen for 20 min. The reaction mixture was then stirred vigorously at 150 °C for 5 h. The reaction mixture was cooled to room temperature. Ice-cold saturated aqueous sodium chloride solution was added, followed by ethyl acetate. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and then concentrated under vacuum to give an oily substance, which was purified by column chromatography to give a product (4.79 g, 48%) as an orange solid.

[0415] Synthesis of 10-(tert-butyl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0416]

[0417] Under nitrogen atmosphere, palladium / carbon (2.227 g, 2.093 mmol, 10 wt%) was added to a 1 L round-bottom flask equipped with a condenser and diaphragm to a suspension of 8-(tert-butyl)-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (8.8 g, 20.93 mmol) in methanol (325 ml), followed by the addition of hydrazine hydrate (26.1 ml, 419 mmol). The mixture was stirred vigorously overnight under nitrogen atmosphere at 65 °C. The mixture was filtered through a diatomaceous earth septum and washed with methanol and dichloromethane. A pale orange solid was obtained, which was purified by column chromatography to a product (7.29 g, 89%) as a grayish-white solid.

[0418] Synthesis of 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononaten-8-amine

[0419]

[0420] A mixture of 10-(tert-butyl)-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (2.0 g, 5.12 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (2.66 g, 5.63 mmol), and BINAP Pd Gen3 (0.254 g, 0.256 mmol) in anhydrous toluene was bubbled under nitrogen for 30 min. Sodium 2-methylprop-2-ol (0.984 g, 10.24 mmol) was added, and the reaction mixture was then refluxed for 20 h. The reaction mixture was quenched with saturated ammonium chloride and diluted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by column chromatography to obtain 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononatenite-8-amine (3 g, 75%) as a grayish-white solid.

[0421] Synthesis of 3-(tert-butyl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium chloride

[0422]

[0423] Hydrochloric acid (0.533 ml, 6.15 mmol) was added to a solution of 10-(tert-butyl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (3 g, 3.84 mmol) in triethyl orthoformate (32.0 ml, 192 mmol). The reaction mixture was heated at 100 °C for two hours. The volatiles were removed under reduced pressure, and the residue was wet-milled with hexane to give a product (2.7 g, 85%) as a grayish-white solid.

[0424] Synthesis of Launcher 5

[0425]

[0426] A mixture of potassium tetrachloroplatinate(II) (1.104 g, 2.66 mmol), the ligand (2.0 g, 2.417 mmol), and 2,6-dimethylpyridine (0.929 ml, 7.98 mmol) in glacial acetic acid (48.3 ml) was bubbled under nitrogen for 40 minutes. The reaction mixture was then refluxed overnight. The reaction mixture was diluted with a methanol / water mixture. The precipitate was filtered off, washed on a filter, and dried. The product (1.1 g) was purified by column chromatography to give a yellow solid.

[0427] Synthesis of Launcher 6

[0428] Synthesis of N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0429]

[0430] Sodium tert-butoxide (3.27 g, 34.0 mmol), 9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (3.77 g, 11.27 mmol), and 2-(3-chlorophenoxy)-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (6.5 g, 11.34 mmol) were added to a 250 mL round-bottom flask and purged with nitrogen. Toluene (90 mL) was added, and the reaction mixture was heated to 80 °C. Then, SphosPdG3 (0.442 g, 0.567 mmol) was added, and the reaction mixture was refluxed. After 2 hours, the reaction mixture was cooled, filtered through diatomaceous earth, and purified by column chromatography to give a purple solid (8 g, 79%).

[0431] Synthesis of 1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium

[0432]

[0433] N-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (8 g, 9.18 mmol) was dissolved in triethoxymethane (24 mL, 144 mmol), refluxed, and cooled to room temperature. Hydrogen bromide (1.341 mL, 11.94 mmol) was then added, and after two hours, a suspension was obtained. The suspension was heated to 65 °C and MTBE (50 mL) was added. The suspension was cooled, and the product was purified by column chromatography to give a grayish-white solid (2.5 g, 28.3%).

[0434] Synthesis of Launcher 6

[0435]

[0436] A mixture of Pt(acac)2 (2.1 g, 5.34 mmol), 2,6-dimethylpyridine (0.292 mL, 2.52 mmol), and 2-bromo-1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1,2-dihydro-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene (2.02 g, 2.1 mmol) in AcOH (20 mL) was bubbled with nitrogen and the reaction mixture was then heated to reflux overnight. The reaction mixture was cooled to room temperature and water was added to give a precipitate. The precipitate was purified by column chromatography to give a yellow solid (0.96 g, 46%).

[0437] Synthesis of Launcher 7

[0438] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0439]

[0440] A mixture of 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (2.59 g, 5.12 mmol), 10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (2.0 g, 4.87 mmol), and sodium 2-methylprop-2-ol (0.936 g, 9.74 mmol) was bubbled under nitrogen, followed by the addition of BINAP-PdG3 (0.242 g, 0.244 mmol). The reaction mixture was heated overnight at 95 °C. The reaction mixture was quenched with saturated ammonium chloride. The resulting slurry was filtered through a diatomaceous earth plunger and washed with dichloromethane. The filtrate was fractionally dissolved between water and DCM, and the aqueous layer was extracted three times with DCM. The combined organic layers were dried over sodium sulfate and purified by column chromatography to give a grayish-white solid (2.43 g, 59%).

[0441] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium chloride

[0442]

[0443] Hydrochloric acid (0.388 ml, 4.65 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (2.43 g, 2.91 mmol) and triethyl orthoformate (24.22 ml, 145 mmol). The reaction mixture was heated at 100 °C for one hour. The solvent was removed under reduced pressure, and the residue was wet-milled with heptane and dried under vacuum to give a grayish-white solid (1.8 g, 70.2%).

[0444]

[0445] A mixture of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-1-onium chloride (1.8 g, 2.041 mmol), potassium tetrachloroplatinate(II) (0.932 g, 2.245 mmol), and 2,6-dimethylpyridine (0.785 ml, 6.74 mmol) in acetic acid (40.8 ml) was bubbled under nitrogen. The reaction mixture was then refluxed overnight. The reaction mixture was cooled to room temperature and water was added to give a precipitate. The precipitate was filtered off, and the filter cake was washed with water and dried by suction filtration. The solid was purified by column chromatography to give a yellow solid (1.2 g, 56.6%).

[0446] Synthesis of Launcher 7

[0447]

[0448] Potassium phosphate hydrate (0.532 g, 2.311 mmol) was bubbled under nitrogen in 1,4-dioxane (7.43 ml) and water (0.825 ml). Platinum complex (0.6 g, 0.578 mmol), SPhos-PdG2 (0.048 g, 0.058 mmol), and (phenyl-) d 5) Boric acid (0.293 g, 2.311 mmol). The resulting slurry was bubbled with nitrogen and the reaction mixture was heated at 100°C overnight. The reaction mixture was cooled to room temperature and the solvent was removed under vacuum. The product was purified by column chromatography to give a yellow solid (0.44 g, 70.2%).

[0449] Synthesis of Launcher 8

[0450]

[0451] Add (4-(tert-butyl)phenyl)boronic acid (0.411 g, 2.311 mmol), SPhos-PdG2 (0.042 g, 0.058 mmol), and potassium phosphate monohydrate (0.532 g, 2.311 mmol) present in a mixture of 1,4-dioxane (5.59 ml) and water (0.621 ml) (10:1) to a 20 mL vial equipped with a stir bar. The mixture was bubbled with nitrogen and then heated to 100 °C overnight. The reaction mixture was cooled to room temperature and filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure and purified by column chromatography to give a yellow solid (0.58 g, 88%).

[0452] Synthesis of Launcher 9

[0453]

[0454] Add (3,5-di-tert-butylphenyl)boronic acid (0.541 g, 2.311 mmol), SPhos-PdG2 (0.042 g, 0.058 mmol), and potassium phosphate monohydrate (0.532 g, 2.311 mmol) present in a mixture of 1,4-dioxane (5.59 ml) and water (0.621 ml) (10:1) to a 20 mL vial equipped with a stir bar. The reaction mixture was bubbled under nitrogen and heated to 100 °C overnight. The mixture was cooled to room temperature and filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure and purified by column chromatography to give a yellow solid (0.61 g, 87%).

[0455] Synthesis of Launcher 10

[0456] Synthesis of 2'-bromo-2-fluoro-3-nitro-1,1'-biphenyl

[0457]

[0458] (2-Bromophenyl)boric acid (21.90 g, 106 mmol), 1-bromo-2-fluoro-3-nitrobenzene (25 g, 111 mmol), sodium carbonate (47.2 g, 445 mmol), Pd(PPh3)4 (6.43 g, 5.57 mmol), toluene (255 mL), ethanol (85 mL), and water (170 mL) were introduced into a 1 L round-bottom flask. The reaction mixture was purged with nitrogen for 30 minutes while being vigorously stirred, and then stirred overnight at 85 °C. The reaction mixture was cooled to room temperature. After the addition of water, the two layers were separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The product was purified by column chromatography to give a white solid (86 g, 91%).

[0459] Synthesis of 2-chloro-2"-fluoro-3-methoxy-3"-nitro-1,1':2',1"-biphenyl

[0460]

[0461] 2'-Bromo-2-fluoro-3-nitro-1,1'-biphenyl (40.4 g, 137 mmol), (2-chloro-3-methoxyphenyl)boronic acid (25 g, 130 mmol), SPhosPdG2 (2.81 g, 3.90 mmol), tetrahydrofuran (600 mL), and potassium phosphate (800 mL, 400 mmol, 0.5 M in water) were introduced into a 2 L round-bottom flask. The reaction mixture was purged with nitrogen for 30 min and then stirred at 60 °C under nitrogen for 5 h. The reaction mixture was cooled to room temperature. After adding water (1 L), the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude substance was purified by column chromatography to give a white solid (80.3 g, 95%).

[0462] Synthesis of 2'"-Fluoro-6'-Methoxy-3"'-Nitro-[1,1':2',1":2",1"'-p-Tetraphenyl]-2-amine

[0463]

[0464] 2-Chloro-2"-fluoro-3-methoxy-3"-nitro-1,1':2',1"-bitriphenyl (40 g, 112 mmol), dioxane (450 mL), and 0.5 M potassium phosphate (700 mL, 350 mmol) were introduced into a 2 L round-bottom flask. The reaction mixture was purged with nitrogen for 30 min. Then, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline (62.5 g, 280 mmol) and SPhosPdG2 (4.11 g, 5.59 mmol) were added, and the reaction mixture was stirred at 90 °C for 16 h. The reaction mixture was cooled to room temperature. After adding water (2 L) and ethyl acetate (500 mL), the two layers were separated. The layers were compared with those obtained by adding ethyl acetate (3 × 500 mL). The aqueous layer was extracted (mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude substance was purified by column chromatography to give a grayish-white solid (61.3 g, 67%).

[0465] Synthesis of 4-methoxy-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0466]

[0467] Cesium carbonate (61.0 g, 185 mmol) was added to a 2 L round-bottom flask containing 2"'-fluoro-6'-methoxy-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine (28 g, 61.8 mmol) in anhydrous DMSO (1 L), and the flask was purged with nitrogen. The reaction mixture was then stirred at 160 °C for three hours. The reaction mixture was allowed to cool to room temperature. 4 L of ice-cold saturated NaCl solution was added, followed by 750 mL of ethyl acetate, and the two layers were separated. The aqueous layer was extracted with ethyl acetate (4 × 500 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum at 45 °C to give a deep red viscous oil. The crude substance was purified by column chromatography to give an orange solid (51.4 g, 85%).

[0468] Synthesis of 10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononaten-4-ol

[0469]

[0470] In a 1 L round-bottom flask, 4-methoxy-10-nitro-9-phosphate hydrochloride (200 g, 1731 mmol) was added to a liquid solution heated at 165 °C with stirring. H -Tetrabenzo[b,d,f,h]azacyclononazone (20 g, 50.7 mmol). The reaction mixture was stirred at 170 °C for four hours. After four hours, the hot solution was poured directly into water (1 L). The resulting suspension was filtered and washed with water (2 × 200 mL) to give a brown solid. The crude substance was purified by column chromatography to give a red solid (35.7 g, 68%).

[0471] Synthesis of 10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononaten-4-yl ester of trifluoromethanesulfonate

[0472]

[0473] Introduce 10-nitro-9 into a 2 L round-bottom flask HTetrabenzo[b,d,f,h]azacyclononaten-4-ol (25 g, 63.7 mmol) and anhydrous dichloromethane (600 mL). The flask was purged with nitrogen, and then triethylamine (17.77 mL, 127 mmol) was added. The reaction mixture was stirred at room temperature for 15 minutes, and then cooled to 0 °C using an ice-water bath. Trifluoromethanesulfonic anhydride (11.26 mL, 66.9 mmol) was then added dropwise over 50 minutes. The reaction mixture was allowed to slowly warm to room temperature and stirred at room temperature for 16 hours. A saturated aqueous solution of sodium bicarbonate (1 L) was added, and the two layers were separated. The aqueous layer was extracted with dichloromethane (3 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude substance was purified by column chromatography to give an orange solid (50.7 g, 97%).

[0474] Synthesis of 10-nitro-4-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0475]

[0476] To a 1 L round-bottom flask, 15 g (29.3 mmol) of 10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononaten-4-yl ester (phenylboronic acid 7.14 g, 58.5 mmol), 0.633 g (0.878 mmol), 135 mL of tetrahydrofuran, and 180 mL (90 mmol, 0.5 M in water) of potassium phosphate were introduced. The flask was purged with nitrogen for 20 min, and the reaction mixture was stirred at 60 °C under nitrogen for 3 h. After 3 h, the reaction mixture was cooled to room temperature. After adding water (500 mL), the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 250 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The crude substance was purified by column chromatography to give a red solid (16.8 g, 96%).

[0477] Synthesis of 14-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0478]

[0479] Under nitrogen atmosphere, Pd / C (4.06 g, 3.81 mmol) was added to a 2 L round-bottom flask containing a suspension of 8-nitro-4-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (16.8 g, 38.1 mmol) in methanol (650 mL), followed by the addition of hydrazine hydrate (47.5 mL, 763 mmol). The mixture was stirred under nitrogen atmosphere at 66 °C for 2 hours. After 2 hours, the reaction mixture was cooled to room temperature. The mixture was filtered through a diatomaceous earth septum, washed with methanol (100 mL), and then washed with dichloromethane (4 × 200 mL). The filtrate was concentrated under vacuum, and the resulting solid was purified by column chromatography to give a grayish-white solid (15.42 g, 97%).

[0480] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-14-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononaten-8-amine

[0481]

[0482] A mixture of 10-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (1.5 g, 2.60 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.756 g, 3.39 mmol), and BINAPPdG3 (0.153 g, 0.154 mmol) in anhydrous toluene was bubbled under nitrogen for 30 min. Sodium 2-methylprop-2-ol (0.592 g, 6.17 mmol) was then added, and the reaction mixture was refluxed for 20 h. The crude mixture was filtered through diatomaceous earth, washed with DCM (25 mL), and concentrated under reduced pressure to give a pale green solid (3.4 g, 87%).

[0483] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-7-phenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium

[0484]

[0485] Hydrochloric acid (0.531 ml, 6.37 mmol) was added to a mixture of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-13-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (3.4 g, 4.24 mmol) and triethyl orthoformate (21.20 ml, 127 mmol). The reaction mixture was heated at 100 °C for one hour. The solvent was removed under reduced pressure, and the residue was wet-milled with heptane and dried under vacuum to give a grayish-white solid (3.0 g, 83%).

[0486] Synthesis of Launcher 10

[0487]

[0488] A mixture of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-6-phenyl-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]ind-1-onium chloride (2.5 g, 2.95 mmol), potassium tetrachloroplatinate(II) (1.347 g, 3.24 mmol), and 2,6-dimethylpyridine (1.134 ml, 9.73 mmol) in acetic acid (59.0 ml) was bubbled under nitrogen for 40 minutes. The mixture was then refluxed overnight. The mixture was cooled to room temperature and a mixture of water and methanol was added. The precipitate was collected by filtration and purified by column chromatography to give a yellow solid (2.6 g, 87%).

[0489] Synthesis of Launcher 11

[0490] Synthesis of 2-fluoro-3"-methoxy-3-nitro-[1,1':2',1":2",1"':3"',1""-pentaphenyl]-2"'-amine:

[0491]

[0492] Under nitrogen atmosphere, potassium phosphate (480 ml, 240 mmol) was added to a suspension of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)-[1,1'-biphenyl]-2-amine (23.60 g, 80 mmol), 2-chloro-2"-fluoro-3-methoxy-3"-nitro-1,1':2',1"-triphenyl (14.3 g, 40.0 mmol), and SphosPdG2 (1.440 g, 1.999 mmol) in dioxane (240 ml). The reaction mixture was heated to 90 °C and maintained for three hours. After cooling, the reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (50 mL). The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layers were concentrated under vacuum, and the residue was purified by column chromatography to give the desired product (13.4 g, 68%).

[0493] Synthesis of 4-methoxy-10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0494]

[0495] A mixture of 2-fluoro-3"-methoxy-3-nitro-[1,1':2',1":2",1"':3"',1"'-pentaphenyl]-2"'-amine (13.4 g, 27.3 mmol) and cesium carbonate (26.7 g, 82 mmol) in DMSO (500 mL) was heated to 150 °C and maintained for three hours. After cooling, the reaction mixture was quenched with water (300 mL) and then extracted with ethyl acetate (300 mL). The organic layer was collected and the aqueous layer was extracted with ethyl acetate (300 mL). The organic layers were combined and concentrated, and the residue was purified by column chromatography to give the desired product (8.76 g, 68%) as an orange solid.

[0496] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononaten-4-ol

[0497]

[0498] A mixture of pyridine hydrochloride (246 g, 2125 mmol) and 4-methoxy-10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (10 g, 21.25 mmol) was heated to 165 °C and maintained for three hours. After cooling, water (200 mL) and ethyl acetate (200 mL) were added with stirring. The organic layer was collected, and the solvent was removed. The residue was purified by column chromatography to give an orange powder (6.5 g, 67%).

[0499] Synthesis of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononaten-4-yl ester of trifluoromethanesulfonate

[0500]

[0501] At 0 °C, trifluoromethanesulfonic anhydride (8.65 g, 30.7 mmol) was added to a solution of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraen-4-ol (7 g, 15.33 mmol) and triethylamine (4.66 g, 46.0 mmol) in CH₂Cl₂ (200 mL). The reaction mixture was then diluted with CH₂Cl₂ (100 mL) and washed with water (100 mL × 2). The solvent was then removed, and the residue was purified by column chromatography to give an orange solid (8.1 g, 90%).

[0502] Synthesis of 10-nitro-4,8-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0503]

[0504] Under nitrogen atmosphere, an aqueous solution of potassium phosphate (122 ml, 61.2 mmol) was added to a solution of 10-nitro-8-phenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-4-yl ester (3.6 g, 6.12 mmol), phenylboronic acid (1.492 g, 12.23 mmol), and SphosPdG2 (0.220 g, 0.306 mmol) in dioxane (60 ml). The reaction mixture was heated to 80 °C and maintained for three hours. After cooling, ethyl acetate (100 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with dichloromethane (100 mL). The combined organic layers were concentrated, and the residue was purified by column chromatography to give the desired compound (2 g, 60%).

[0505] Synthesis of 10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0506]

[0507] A mixture of 10-nitro-4,8-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (2 g, 3.87 mmol), hydrazine hydrate (3.88 g, 77 mmol), and palladium (0.412 g, 0.387 mmol) on carbon in EtOH (200 mL) and CH₂Cl₂ (20 mL) was heated to 90 °C and maintained for three hours. After cooling, the reaction mixture was filtered through diatomaceous earth and washed with ethyl acetate. All solvents were removed, and the residue was purified by column chromatography to give the desired product (1.2 g, 63%).

[0508] Synthesis of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0509]

[0510] A mixture of 10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (1.5 g, 3.08 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.756 g, 3.39 mmol), and BINAP PdGen3 (0.153 g, 0.154 mmol) in anhydrous toluene was bubbled under nitrogen for 30 min. Sodium 2-methylprop-2-ol (0.592 g, 6.17 mmol) was added, and bubbling continued for 10 min. The reaction mixture was then refluxed for 20 h. The crude mixture was filtered through diatomaceous earth, washed with DCM (25 mL), and concentrated under reduced pressure to give a pale green solid (1.8 g, 58%).

[0511] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-3,7-diphenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium

[0512]

[0513] HCl (0.222 ml, 7.30 mmol) was added to a solution of N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-10,14-diphenyl-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (4 g, 4.56 mmol) in triethyl orthoformate (38.0 ml, 228 mmol). The reaction mixture was heated at 100 °C for 3 hours, resulting in complete inversion. The volatiles were removed under reduced pressure to give a white solid (5.1 g, 4.25 mmol, 93%).

[0514] Synthesis of Launcher 11

[0515]

[0516] A mixture of potassium tetrachloroplatinate (2.52 g, 6.07 mmol), 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3,7-diphenyl-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium chloride (5.1 g, 5.52 mmol) and 2,6-dimethylpyridine (2.100 ml, 18.22 mmol) in AcOH (110 ml) was bubbled under nitrogen for 40 minutes. The reaction mixture was then refluxed at 120 °C for 18 hours. The combined mixture was diluted with water (150 mL) and extracted with DCM (3 × 150 mL). The crude substance was concentrated and the product was purified by column chromatography to obtain a yellow solid (1.2 g, 18.11%).

[0517] Synthesis of Launcher 12

[0518] Synthesis of 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline

[0519]

[0520] Under nitrogen atmosphere, Pd(dppf)Cl2 was added to a suspension of 2-bromo-6-chloroaniline (8.2 g, 39.7 mmol), bis(pinacolyl)diboron (30.3 g, 119 mmol), and KOAc (15.59 g, 159 mmol) in DMSO (80 mL). CH₂Cl₂ (1.622 g, 2 mmol). The reaction mixture was then heated to 90 °C and maintained at this temperature for 20 hours under nitrogen. After cooling, ethyl acetate (200 mL) and an aqueous HCl solution (0.5 M, 100 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed with brine (100 mL × 2). The organic solution was then dried over Na₂SO₄. After solvent removal, the residue was purified by column chromatography to give a white solid (8.1 g, 80%).

[0521] Synthesis of 2-(2'-bromo-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane

[0522]

[0523] Under nitrogen atmosphere and at -78°C, n-BuLi (23 mL, 2.5 M, 27.5 mmol) was added dropwise to a solution of 2,2'-dibromo-1,1'-biphenyl (15 g, 48.1 mmol) in anhydrous THF (500 mL). After the addition, the reaction mixture was stirred for 1 hour, and then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoboronyl pentane (11.63 g, 62.5 mmol) in anhydrous THF (10 mL) was slowly added at -78°C. After the addition, the reaction temperature was gradually lowered to room temperature and stirred for another 2 hours. Water (200 mL) and ethyl acetate (200 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (200 mL). The combined organic layer solvent was removed, and the residue was purified by column chromatography to give the desired product (11 g, 64%).

[0524] Synthesis of 2"-bromo-2-fluoro-3-nitro-1,1':2',1"-biterphenyl

[0525]

[0526] Under nitrogen, Pd(Ph3P)4 (2.028 g, 1.755 mmol) was added to a suspension of 1-bromo-2-fluoro-3-nitrobenzene (10.04 g, 45.6 mmol), borate ester 268-4 (12.6 g, 35.1 mmol), and K2CO3 aqueous solution (70.2 mL, 2M, 140.4 mmol) in dioxane (140 mL). The reaction mixture was heated to 85 °C overnight under nitrogen. After cooling, ethyl acetate (150 mL) and water (150 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (150 mL). The combined organic layer solvent was removed, and the residue (9 g, 68%) was purified by column chromatography.

[0527] Synthesis of 3-chloro-2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine

[0528]

[0529] Under N2, an aqueous solution of K3PO4 (103 mL, 0.5 M, 51.6 mmol) was added to a solution of 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)aniline (2.4 g, 9.46 mmol), 2"-bromo-2-fluoro-3-nitro-1,1':2',1"-bitriphenyl (3.2 g, 8.6 mmol), and SphosPdG2 (0.31 g, 0.43 mmol) in THF (55 mL). The reaction mixture was heated to 60 °C and maintained for 3 hours. After cooling, ethyl acetate (50 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layer solvent was removed. The residue was purified by column chromatography to give the desired product (2.8 g, 78%).

[0530] Synthesis of 8-chloro-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0531]

[0532] Cs₂CO₃ (17.5 g, 53.7 mmol) was added to a solution of 3-chloro-2"'-fluoro-3"'-nitro-[1,1':2',1":2",1"'-p-tetraphenyl]-2-amine (7.5 g, 17.9 mmol) in DMSO. The reaction mixture was heated to 150 °C (oil bath temperature) and maintained for 3 h. After cooling, the reaction mixture was quenched with water (100 mL) and then extracted with ethyl acetate (100 mL × 2). The combined organic solutions were washed with brine (100 mL × 2). The solvent was then removed under vacuum, and the residue was purified by column chromatography to give an orange solid product (5.2 g, 72.8%).

[0533] Synthesis of 8-([1,1':3',1"-terphenyl]-5'-yl)-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononazone

[0534]

[0535] Under N2 conditions, an aqueous solution of K3PO4 (211 mL, 0.5 M, 105 mmol) was added to a suspension of 8-chloro-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (6 g, 15.04 mmol), terphenylboronic acid 268-8 (8.25 g, 30.1 mmol), and SphosPdG2 (1.084 g, 1.5 mmol) in dioxane (100 mL). The reaction mixture was heated to 90 °C and maintained for three hours. After cooling, ethyl acetate (100 mL) and water (50 mL) were added with stirring. The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were solvent-removed, and the residue was purified by column chromatography to give a solid product (8.92 g, 100%).

[0536] Synthesis of 10-([1,1':3',1"-triphenyl]-5'-yl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine

[0537]

[0538] Pd / C (1 g, 10%, 0.945 mmol) was added to a solution of 8-([1,1':3',1"-triphenyl]-5'-yl)-10-nitro-9H-tetrabenzo[b,d,f,h]azacyclononatetraene (2.8 g, 4.72 mmol) and hydrazine hydrate (11.82 g, 236 mmol) in a mixed solvent system of ethanol (100 mL) and CH2Cl2 (20 mL). The reaction mixture was heated to reflux and maintained for 3 hours. After cooling, the reaction mixture was filtered through diatomaceous earth and washed with CH2Cl2 (20 mL × 5). The solvent was removed, and the residue was purified by column chromatography to give a grayish-white solid product (1.35 g, 50%).

[0539] Synthesis of 10-([1,1':3',1"-triphenyl]-5'-yl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononaten-8-amine:

[0540]

[0541] A mixture of 10-([1,1':3',1"-Bis(phenyl)-5'-yl)-9H-tetrabenzo[b,d,f,h]azacyclononatetraene-8-amine (1.5 g, 2.67 mmol), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.519 g, 2.93 mmol), and BINAPPdG3 (0.132 g, 0.133 mmol) in anhydrous toluene was bubbled under nitrogen for 30 min. Sodium 2-methylprop-2-ol (0.512 g, 5.33 mmol) was then added, and bubbling continued for 10 min. The reaction mixture was then refluxed for 20 h. The reaction mixture was quenched with saturated ammonium chloride (20 mL) and diluted with ethyl acetate (20 mL). The resulting slurry was filtered through a diatomaceous earth plunger (0.5"). The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (2 × 20 mL). The combined organic layers were washed with saturated brine (50 mL), dried over anhydrous sodium sulfate (12 g), and concentrated. The residue was purified by column chromatography to give a grayish-white solid (2.32 g, 89%).

[0542] Synthesis of 3-([1,1':3',1"-triphenyl]-5'-yl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium

[0543]

[0544] HCl (0.118 ml, 3.89 mmol) was added to a solution of 10-([1,1':3',1"-triphenyl]-5'-yl)-N-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-9H-tetrabenzo[b,d,f,h]azacyclononazone-8-amine (2.32 g, 2.434 mmol) in triethyl orthoformate (20.26 ml, 122 mmol). The reaction mixture was heated at 100 °C for 16 hours. The volatiles were removed under reduced pressure and the residue was wet-milled with warm hexane (2 × 25 mL) to give a grayish-white solid (2.35 g, 85% yield).

[0545] Synthesis of Launcher 12

[0546]

[0547] Potassium tetrachloroplatinate (0.228 g, 0.550 mmol), 3-([1,1':3',1"-triphenyl]-5'-yl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-yl)oxy)phenyl)-1H-1,2a-diazatribenzo[4,5:6,7:8,9]cyclononatetraen[1,2,3-cd]indene-2a-onium chloride (0.5 g, 0.500 mmol) and 2,6-dimethylpyridine (0.190 ml, 1.651 mmol) in AcOH (10.00 The mixture in ml was bubbled with nitrogen for 40 minutes. The reaction mixture was refluxed at 120°C overnight. The reaction mixture was diluted with water and the aqueous layer was extracted several times with DCM. The organic layers were combined, dried and concentrated, and the residue was purified by column chromatography to give a yellow solid (1.6 g, 73%).

[0548] Device data

[0549] To compare the performance of some examples of compounds of the present invention relative to comparative compounds in OLED applications, eight OLED devices were manufactured. OLED 1 to OLED 7 respectively contain emitters 2, 3, 6, 4, 5 and 7 of the present invention as their emitter compounds, and OLED 8 contains a comparative compound as its emitter compound. Device performance data are shown in Table 1 below.

[0550] The OLED is grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer with a sheet resistivity of 15 Ω / sq. Before any organic layer is deposited or coated, the substrate is degreased with a solvent, then treated with oxygen plasma at 100 mTorr and 50 W for 1.5 minutes and with UV ozone for 5 minutes.

[0551] Through thermal evaporation in a high vacuum (<10) -6 OLEDs are fabricated in a cathode (Al). The anode electrode is 750 Å indium tin oxide (ITO). Starting from the ITO surface, the organic layers of the device example consist sequentially of: 100 Å compound 1 (HIL), 250 Å compound 2 (HTL), 50 Å compound 3 (EBL), 300 Å compound 3 (EML) doped with 50% compound 4 and 12% emitter, 50 Å compound 4 (BL), 300 Å compound 5 (ETL) doped with 35% compound 6, 10 Å compound 5 (EIL), followed by 1,000 Å Al (cathode). All devices, immediately after fabrication, are encapsulated in a nitrogen glove box (H2O and O2 < 1 ppm) with a glass lid, sealed with epoxy resin, and the encapsulation includes a desiccant. Doping percentages are volume percentages.

[0552] Table 1: Overview of OLED Performance

[0553]

[0554]

[0555] The following compounds are used in the device:

[0556]

[0557] This application discloses N-heterocyclic carbene platinum (NHC) complexes characterized by a carbene-N substituent attached to or "tied" to the back of the NHC. Compared to comparative compounds in which the carbene-N phenyl substituent is not tied to the carbene, binding the carbene-N substituent significantly improves photophysical properties and device performance. In most cases, the spectral shape of the bound NHC is much narrower than that of the comparative compounds that achieve improved color purity. Generally, phosphorescent emitter complexes have a broad emission spectrum with a wide field of view (FWHM), typically greater than 50 nm, as shown in the comparative examples herein. Achieving a narrow FWHM has been a long-sought goal. The narrower the FWHM, the better the color purity for display applications. In previous OLED research, narrower line shapes have been gradually achieved nanometer by nanometer. As can be seen here, the bound compounds of this invention can significantly reduce the FWHM value to below 40 nm or even 30 nm. The compounds of this invention have also been blue-shifted to a more desired deeper blue, thereby enabling more efficient devices and purer colors. Another significant improvement is that the binding compounds in almost all examples nearly doubled the device efficiency. Such improvements are considered substantial and represent a major step towards the commercialization of these inventive emitters. Given that the inventive compound examples (emitters 2, 3, 4, 5, 6, 7, and 13) have similar structures to the comparative compounds, differing only in the additional binding portion, the observed significant performance improvements are unexpected.

Claims

1. An organic light-emitting device (OLED) comprising: anode; cathode; and An organic layer disposed between the anode and the cathode. The organic layer contains a ligand L with the following formula: A compounds Formula I , or Formula II , in: Ring A is independently a 5- to 10-membered heterocyclic ring; X 1 To X 6 Each can be either C or N independently; K 3 It is a direct bond, O, or S; R A R B and R C Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof. in: The ligand L A It is connected to the metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; The ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and Any two adjacent R A R B R C Or R 1 They can be connected or fused to form rings; At least one of the following conditions is true: (1) The compound is a sensitizer, and the OLED further comprises a receptor selected from the group consisting of fluorescent emitters, delayed fluorescent emitters and combinations thereof; (2) At least one of the anode, the cathode, or a new layer disposed above the organic emission layer serves as a reinforcement layer; wherein the reinforcement layer comprises a plasma material exhibiting surface plasmon resonance, the plasma material being nonradiatively coupled to the compound and transferring the excited state energy of the compound to the nonradiative mode of the surface plasmon polariton.

2. The OLED according to claim 1, wherein X 1 To X 6 Each is C.

3. The OLED according to claim 1, wherein at least two adjacent R A Substituents are linked to form a ring that fused with ring A.

4. The OLED according to claim 1, wherein when ring A is a 7-element, 8-element, 9-element, or 10-element ring, four adjacent R A Substituents connect to form two fused rings fused with ring A; or, when ring A is an 8-, 9-, or 10-membered ring, a total of 6 adjacent Rs are formed. A The substituents connect to form three separate rings, each fused to ring A.

5. The OLED according to claim 1, wherein the ligand L A Choose from the following groups: , , , , , , , , and , Among them, ring A1 is independently a 5- to 10-membered heterocyclic ring; rings A2, A3, A4, A5, B2 and B3 are each independently a 5- or 6-membered carbon ring or heterocyclic ring; and ring B1 is independently a 5-, 6- or 7-membered carbon ring or heterocyclic ring.

6. The OLED according to claim 1, wherein the ligand L A Choose from the following groups: , , , , , , , , , , , , , , , , and , Each Q is independently C or N; and each W is independently BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO2, C=CRR', CRR', SiRR', or GeRR', wherein R and R' are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof.

7. The OLED of claim 1, wherein the compound has a formula selected from the group consisting of: Ir(L A 3. Ir(L) A (L) B )2、Ir(L A )2(L B ), Ir(L A )2(L C ), Ir(L A (L) B (L) C ) and Pt(L A (L) B ); and L A L B and L C They are different from each other; among them, L A With L B They can be connected to form Pt(L) A (L) B The tetradentate ligand in ); where L B and L C Each member independently chooses from the following groups: , , , , , , , , , , , , , , , , , , , , , and , in: T is chosen from the group consisting of B, Al, Ga, and In; Y 1 To Y 13 Each independently selects a group composed of C and N; Y' selects from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f ; R e With R f They can be fused or joined to form rings; Each R a R b R c and R d Independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and Any two adjacent R a R b R c R d R e and R f They can fused or connected to form rings or form polydentate ligands.

8. The OLED according to claim 1, wherein the compound has the following structure Formula III ,or Formula IV , in: M 1 It is either Pd or Pt; The C and D groups are each independently monocyclic or polycyclic ring structures containing 5-membered and / or 6-membered carbon rings or heterocycles; Z 1 and Z 2 Each can be either C or N independently; K 1 K 2 and K 3 Each independently selects a group consisting of direct keys, O, and S, where K 1 K 2 or K 3 At least two of them are direct bonds; L 1 L 2 and L 3 Each is independently selected from the following groups: direct bond, BR, BRR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, cycloalkyl and combinations thereof, wherein L is present. 1 and L 2 At least one of them; n1, n2, and n3 are each 0 or 1, and n1 + n2 + n3 = 2 or 3; X 7 To X 9 Each can be either C or N independently; R C' and R D Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; R C' and R D Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; Any two adjacent substituents can be linked or fused together to form a ring.

9. The OLED according to claim 8, wherein the C group is a 5- or 6-membered aromatic ring; and the D group is a 6-membered aromatic ring; wherein n1 is 1, and L 1 It is O; where L 2 It is a direct bond or NR'; and where K 1 K 2 and K 3 Each is a direct key; and X 1 To X 9 Both are C.

10. The OLED of claim 8, wherein Z 2 It is N and Z 1 It is C; or Z 2 It is C and Z 1 It is N.

11. The OLED according to claim 8, wherein the compound has the following structure: Formula V , or VI , Z 3 It is C or N; the remaining variables are the same as previously defined; and Any two adjacent substituents can be linked or fused together to form a ring.

12. The OLED according to claim 8, wherein ring C and ring D are each independently benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole.

13. The OLED of claim 8, wherein the compound is selected from the group consisting of List 5 as defined herein: , , , , , , , , , , , , , , , , , , , , and ; in: R x and R y Each is selected from the following groups: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; R G Each time it appears, it is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and Any two adjacent substituents can be linked or fused together to form a ring.

14. The OLED of claim 1, wherein the organic layer further comprises a body, wherein the body comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5,9-dioxa-13b-boronanaphthalene[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenene, and aza-(5,9-dioxa-13b-boronanaphthalene[3,2,1-de]anthracene).

15. A consumer product including an organic light-emitting device (OLED), said organic light-emitting device comprising: anode; cathode; and An organic layer disposed between the anode and the cathode. The organic layer contains a ligand L with the following formula: A compounds Formula I , or Formula II , in: Ring A is independently a 5- to 10-membered heterocyclic ring; X 1 To X 6 Each can be either C or N independently; K 3 It is a direct bond, O, or S; R A R B and R C Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R1, R A R B R C Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, selenalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof. in: The ligand L A It is connected to metal M via two designated dashed lines; M is Ru, Os, Ir, Pd, Pt, Cu, Ag, or Au, and can coordinate with other ligands; The ligand L A It can connect with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and Any two adjacent R A R B R C or R 1 They can connect or fuse to form rings. At least one of the following conditions is true: (1) The compound is a sensitizer, and the OLED further comprises a receptor selected from the group consisting of fluorescent emitters, delayed fluorescent emitters and combinations thereof; (2) At least one of the anode, the cathode, or a new layer disposed above the organic emission layer serves as a reinforcement layer; wherein the reinforcement layer comprises a plasma material exhibiting surface plasmon resonance, the plasma material being nonradiatively coupled to the compound and transferring the excited state energy of the compound to the nonradiative mode of the surface plasmon polariton.

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