Tetradentate platinum and palladium complex emitters

Abstract

The invention relates to a tetradentate platinum and palladium complex emitter. A series of novel tetradentate platinum (II) and palladium (II) complexes based on bulky substituents have been designed. These complexes can act as emitters in organic electroluminescent devices.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the following U.S. Provisional Applications: U.S. Provisional Application No. 63 / 613,283 filed on December 21, 2023, U.S. Provisional Application No. 63 / 611,414 filed on December 18, 2023, U.S. Provisional Application No. 63 / 606,270 filed on December 5, 2023, U.S. Provisional Application No. 63 / 606,265 filed on December 5, 2023, and U.S. Provisional Application No. 63 / 606,247 filed on December 5, 2023, all of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present application relates to tetradentate platinum and palladium complex emitters. Background Art

[0004] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (such as their flexibility) can make them more suitable for specific applications, such as manufacturing on flexible substrates. Examples of organic optical electronic devices include organic light emitting diodes (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength of light emitted by the organic emissive layer can generally be easily adjusted with appropriate dopants.

[0005] In recent years, organic light-emitting diodes (OLEDs) have attracted great attention in academia and industry due to their outstanding advantages, such as high color quality, wide viewing angle, low-cost manufacturing, low power consumption, fast response speed, and high conversion efficiency of electrons to photons. Most organic light-emitting diodes (OLEDs) are phosphorescent OLEDs using iridium (Ir), palladium (Pd), and platinum (Pt) complexes, because these metal complexes have strong spin-orbit coupling (Spin-Orbital Coupling), which can effectively emit light from their triplet excited states (triplet exited state) and achieve almost 100% internal efficiency. The development of efficient and stable narrow-band deep blue emitters has been the most interesting research topic in recent years. Due to the high energy of blue emitters, blue phosphorescent OLEDs suffer from low lifetime.

[0006] There remains a need in the art for efficient and stable OLED assemblies. The present invention addresses this unmet need. Summary of the invention

[0007] In one aspect, the present invention relates to a compound of formula I:

[0008]

[0009] in:

[0010] M represents platinum (Pt) or palladium (Pd);

[0011] X 1 , X 2 , X 3 and X 4 Coordinated to M and independently N or C;

[0012] Cy 1 , Cy 2 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0013] Cy 3 , Cy 6 and Cy 7 is independently present or absent; wherein each Cy 3 , Cy 6 and Cy 7 are independently substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0014] Among them, when Cy 3 If it does not exist, then B 1 Selected from the group consisting of: CR 8 R 9 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 8 R 9 ,GeR 8 R 9 NR 10 , PR 10 , R 10 P=O、AsR 10 , R 10 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 10 ,BiR 10 , R 3 Bi=O、 or B 1 Does not exist and Cy 1With Cy 2 Connect via a single button;

[0015] Among them, when Cy 3 If it exists, then B 1 Selected from the group consisting of: CR 8 、SiR 8 ,GeR 8 ,N,P,P=O,As,As=O,B,R 10 Bi=O or Bi, or B 1 Does not exist and Cy 1 With Cy 2 Connect via a single button;

[0016] Among them, when Cy 6 If it does not exist, then B 2 Selected from the group consisting of: CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 11 R 12 ,GeR 11 R 12 NR 13 , PR 13 , R 13 P=O、AsR 13 , R 13 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 13 ,BiR 13 , R 13 Bi=O、 or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button;

[0017] Among them, when Cy 6 If it exists, then B 2 Selected from the group consisting of: CR 11 、SiR 11 ,GeR 11 ,N,P,P=O,As,As=O,B,R 13 Bi=O or Bi, or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button;

[0018] Among them, when Cy 7 If it does not exist, then A 4does not exist and B 2 Yes A 8 ;

[0019] Among them, when Cy 7 If it exists, then B 2 Selected by CR 14 、SiR 14 ,GeR 14 ,N,P,P=O,As,As=O,B,R 14 Bi=O or Bi;

[0020] A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of is independently absent or present, and A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of the CR 15 R 16 , CR 15 =CR 16 , C≡C, C=O, C=S, SiR 15 R 16 ,GeR 15 R 16 NR 17 , PR 17 , R 17 P=O、AsR 17 , R 17 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 17 ,BiR 17 , R 17 Bi=O、

[0021] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14, R 15 , R 16 , R 17 , R 18 and R 19 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silane, polymeric group; or any conjugate or combination thereof;

[0022] wherein any two adjacent substituents are optionally joined to form a fused ring of Formula A, Formula B, Formula C, or Formula D:

[0023]

[0024] A 6 and A 7 Each of which is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0025] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Each of is independently N, C, P, O, S or Si;

[0026] Each R 7 and R 8 is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 7 and R 8 independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof; wherein any two adjacent substituents may further be joined to form a fused ring; and

[0027] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 One or more of optionally represents R X , where R Xis a bulky substituent selected from the group consisting of branched alkyl, cycloalkyl, bicyclic, fused bicyclic, adamantyl, ferrocenyl, dialkylamino, diarylamino, alkylarylamino, trialkylsilyl, tricycloalkylsilyl, triarylsilyl, triheteroarylsilyl, dialkylarylsilyl, alkyldiarylsilyl, alkylarylamino, and optionally substituted: aryl and heteroaryl.

[0028] In one embodiment, an organic light emitting device (OLED) and / or a consumer product comprising the compound is provided. In one embodiment, a formulation comprising the compound is included. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The following detailed description of the preferred embodiments of the present disclosure will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the present invention, preferred embodiments of the present invention are shown in the accompanying drawings. However, it should be understood that the present invention is not limited to the precise arrangements and means of the embodiments shown in the accompanying drawings.

[0030] Figure 1 is a schematic diagram of an organic light-emitting device.

[0031] Figure 2 is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0032] Figure 3 is a plot of PL intensity versus wavelength for an exemplary compound Pt6O5-m at room temperature and 77K.

[0033] Figure 4 is a plot of PL intensity versus wavelength for an exemplary compound PtON5N-mtbb at room temperature and 77K.

[0034] Figure 5 is a plot of PL intensity versus wavelength for an exemplary compound PtON5-dtb in 2-methyl-THF solution at room temperature and 77 K.

[0035] Figure 6 is a schematic diagram of the triplet energy level of such Pt complexes at room temperature, where T 1 It comes from the phenoxy-carbazole functional group in the PtON5-AR structure, i.e., the blue solid line, and T 1 *Derived from the phenylbenzimidazole-carbene group, i.e. the green long dot-dashed line.

[0036] Figure 7 Schematic diagram of the design of a new emitter capable of narrowing the emission spectrum of a Pt complex by generating intramolecular interactions between the phenyl group and the benzimidazole-carbene group, between the benzimidazole-carbene group and the carbene-bonded aryl group, and between the carbene-bonded aryl group and the pyridyl group. 1* state is unstable or by extending the conjugation level of the carbazole group to make T 1 to achieve state stability.

[0037] Figure 8 It is the room temperature emission spectrum of PtON5-m in dichloromethane solution and the electroluminescence spectrum of a device with the structure of ITO / HATCN (10nm) / NPD (60nm) / SiBCz (5nm) / 10wt% PtON5-m:60wt% SiBCz:30wt% SiTrzCz2 (25nm) / mSiTrzPh (5nm) / BPyTP (40nm) / LiQ / A.

[0038] Fig. 9 The room temperature emission spectra of 10% PtON5-m:SiBCz and 10% PtON5-m:SiTrzCz2 films are shown. The chemical structures of PtON5-m, PtON5-pCz-dtb, SiBCz and SiTrzCz2 are also shown, as well as a schematic diagram of the intermolecular interactions between PtON5-m and SiTrzCz2.

[0039] Fig.10 is a graph of the room temperature emission spectrum of a 10% PtON5-dtb-m:SiTrzCz2 film.

[0040] Fig.11 is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0041] Fig.12 is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0042] Fig.13 is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0043] Fig.14 is a plot of PL intensity versus wavelength for an exemplary compound Pt2O1_pp at room temperature and 77K.

[0044] Fig.15 is a plot of PL intensity versus wavelength for an exemplary compound Pt2O5_N2m at room temperature.

[0045] Fig.16 is a plot of PL intensity versus wavelength for an exemplary compound Pt8O5_N2m_pp at room temperature and 77K.

[0046] Fig.17 It is a schematic diagram of the energy levels where the emission full width at half maximum (FWHM) becomes narrower.

[0047] Fig.18is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0048] Fig.19 is a graph of PL intensity versus wavelength at room temperature for exemplary compounds PtON5S56-m and PtON5S56-mtb. The photoluminescence spectra of exemplary compounds PtON5S56-m and PtON5S56-mtb are presented in Fig.19 The photoluminescence spectra of the exemplary compounds PtON5NS56-m and PtON5S56-dpm are presented in Fig. 20 The photoluminescence spectrum of another exemplary compound is shown in Fig.21 middle.

[0049] Fig. 20 is a plot of PL intensity versus wavelength for exemplary compounds PtON5NS56-m and PtON5S56-dpm at room temperature.

[0050] Fig.21 is a plot of PL intensity versus wavelength for exemplary compounds at room temperature and 77K.

[0051] Fig. 22 is a plot of PL intensity versus wavelength for an exemplary compound Pt3O5-tbm at room temperature. DETAILED DESCRIPTION

[0052] definition

[0053] It should be understood that the drawings and descriptions in the present disclosure have been simplified for the purpose of illustrating relevant elements so as to clearly understand the present invention, and multiple other elements found in technical fields related to phosphorescent organic light-emitting devices, etc., have been eliminated for the purpose of clarity. Those of ordinary skill in the art may recognize that other elements and / or steps may be required and / or necessary to implement the disclosed embodiments. However, because such elements and steps are well known in the art, and because they do not contribute to a better understanding of the present disclosure, a discussion of such elements and steps is not provided herein. The disclosure herein relates to all such changes and modifications to such elements and methods known to those skilled in the art.

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure belongs. Although any methods, materials, and components similar or equivalent to those described herein can be used in the practice or testing of the present invention, preferred methods and materials are now described.

[0055] As used herein, each of the following terms has the meaning associated with it in this section.

[0056] The articles "a" and "an" are used herein to refer to one or more than one (ie, at least one) of the grammatical object of the article. For example, "an element" means one element or more than one element.

[0057] As used herein, "about" when referring to a measurable value such as an amount, a period of time, etc., is intended to encompass deviations of ±20%, ±10%, ±5%, ±1%, or ±0.1% from the particular value, as long as such deviations are appropriate.

[0058] Throughout the present disclosure, aspects of the present disclosure may be presented in a range format. It should be appreciated that the description in a range format is merely for convenience and simplification, and should not be construed as a rigid limitation on the scope of the invention. Therefore, the description of a range should be considered to have specifically disclosed all possible subranges and individual numerical values ​​within the range. For example, a description such as a range from 1 to 6 should be considered to have specifically disclosed subranges, such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numbers within the range, such as 1, 2, 2.7, 3, 4, 5, 5.3, 6, and any complete and partial increments therebetween. This applies regardless of the width of the range.

[0059] Disclosed are components for preparing the compositions of the present disclosure and the compositions themselves used in the methods disclosed herein. These materials and other materials are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, although specific references to various individual and common combinations and arrangements of these compounds are not explicitly disclosed, each of them is specifically considered and described herein. For example, if a specific compound is disclosed and discussed and multiple modifications that can be made to multiple molecules including the compound are discussed, each combination and arrangement of the compound and possible modifications are specifically considered, unless there is a specific description to the contrary. Therefore, if a class of molecules A, B and C and a class of molecules D, E and F are disclosed and an example of a combination molecule AD is disclosed, then even if each is not individually described, each of them is still considered individually and collectively, thereby meaning that it is considered to disclose combinations AE, AF, BD, BE, BF, CD, CE and CF. Similarly, any subset or combination of these is also disclosed. Therefore, for example, it is considered to disclose a subgroup of AE, BF and CE. This concept applies to all aspects of the present application, including (but not limited to) steps in the method of making and using the composition of the present invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the present invention.

[0060] As mentioned herein, a connecting atom or a connecting group can connect two groups, such as N and C groups. If valence permits, the connecting atom can optionally be connected to other chemical moieties. For example, in one aspect, once oxygen is bonded to two groups (such as N and / or C groups), no other chemical groups will be connected because valence is satisfied. In another aspect, when carbon is a connecting atom, two additional chemical moieties can be connected to the carbon. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ═O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl and heterocyclic groups.

[0061] The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, and heterocyclyl groups.

[0062] As used herein, the term "substituted" is considered to include all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For appropriate organic compounds, permissible substituents may be one or more and the same or different. For the purposes of this disclosure, heteroatoms (such as nitrogen) may have hydrogen substituents and / or any permissible substituents of organic compounds described herein, which will satisfy the valence of heteroatoms. This disclosure does not wish to be limited in any way by permissible substituents of organic compounds. In addition, the term "substituted" or "substituted by ... " includes implicit conditions, i.e., such substitution is consistent with the permissible valence of the substituted atom and the substituent, and the substitution produces a stable compound, such as a compound that does not spontaneously undergo transformations such as rearrangement, cyclization, elimination, etc. It is also contemplated that in certain aspects, unless explicitly stated to the contrary, individual substituents may be further optionally substituted (ie, further substituted or unsubstituted).

[0063] The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted by one or more groups (including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxyl, nitro, silane, sulfonic acid-oxo or thiol), as described herein. A "lower alkyl" group is an alkyl group containing one to six (e.g., one to four) carbon atoms.

[0064] Throughout the specification, "alkyl" is generally used to refer to unsubstituted alkyl and substituted alkyl; however, substituted alkyl is also specifically mentioned herein by identifying a specific substituent on the alkyl. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine or iodine). The term "alkoxyalkyl" specifically refers to an alkyl substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl substituted with one or more amino groups, etc., as described below. When "alkyl" is used in one case and a specific term such as "alkyl alcohol" is used in another case, this is not intended to imply that the term "alkyl" also does not refer to a specific term such as "alkyl alcohol" or the like.

[0065] This practice also applies to the other groups described herein. That is, while terms such as "cycloalkyl" refer to unsubstituted and substituted cycloalkyl moieties, substituted moieties may be otherwise specifically identified herein; for example, a specific substituted cycloalkyl may be referred to as, for example, "alkylcycloalkyl." Similarly, a substituted alkoxy may be specifically referred to as, for example, "haloalkoxy," and a specific substituted alkenyl may be, for example, "alkenyl alcohol," etc. Again, the practice of using a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not intended to imply that the general term also does not include the specific term.

[0066] The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring consisting of at least three carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term "heterocycloalkyl" is a type of cycloalkyl as defined above, and is included within the meaning of the term "cycloalkyl", wherein at least one carbon atom in the ring is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkyl and heterocycloalkyl may be substituted or unsubstituted. Cycloalkyl and heterocycloalkyl may be substituted by one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halo, hydroxyl, nitro, silane, sulfonic acid-oxo, or thiol as described herein.

[0067] The term "polyalkylene" as used herein refers to a group having two or more CH 2 The polyalkylene group can be represented by the formula -(CH 2 ) a -, where "a" is an integer from 2 to 500.

[0068] As used herein, the terms "alkoxy" and "alkoxyl" refer to an alkyl or cycloalkyl group bonded through an ether bond; that is, an "alkoxy" group can be defined as -OA 1 , where A 1 is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether, such as -OA 1 -OA 2 or-OA 1 -(OA 2 ) a -OA 3 , where "a" is an integer from 1 to 200 and A 1 , A 2 and A 3 is an alkyl group and / or a cycloalkyl group.

[0069] As used herein, the term "alkenyl" is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. 1 A 2 )C═C(A 3 A 4 ) are intended to include both E and Z isomers. This can be inferred from the structural formula herein where an asymmetric olefin is present, or it can be explicitly represented by the bond symbol C=C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azido, nitro, silanyl, sulfonic acid-oxo or thiol as described herein.

[0070] As used herein, the term "cycloalkenyl" is a non-aromatic carbon-based ring consisting of at least three carbon atoms and containing at least one carbon-carbon double bond (i.e., C=C). Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkenyl" in which at least one of the carbon atoms of the ring is replaced by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups may be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azido, nitro, silanyl, sulfonyl-oxo, or thiol as described herein.

[0071] As used herein, the term "alkynyl" is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon triple bond. Alkynyl groups may be unsubstituted or substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azido, nitro, silanyl, sulfonic acid-oxo or thiol as described herein.

[0072] The term "cycloalkynyl" as used herein is a non-aromatic carbonyl ring consisting of at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, etc. The term "heterocycloalkynyl" is a cycloalkenyl as defined above, and is included in the meaning of the term "cycloalkynyl", wherein at least one carbon atom in the ring is replaced by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl may be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted by one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azide, nitro, silyl, sulfonic acid-oxo or thiol as described herein.

[0073] As used herein, the term "aryl" is a group containing any carbon-based aromatic group, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings can have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one ring is an aromatic hydrocarbon group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic and / or heteroaryl. Preferably, the aryl group is an aryl group containing six to thirty carbon atoms, preferably six to twenty carbon atoms, and more preferably six to twelve carbon atoms. Especially preferred are aryls with six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, phenanthren, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Furthermore, the aryl radical is optionally substituted.

[0074] The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl", also included in the term "aryl", defines a group containing an aromatic group without heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted by one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxyl, ketone, azido, nitro, silane, sulfonic acid-oxo or thiol as described herein. The term "biaryl" is a specific type of aryl and is included in the definition of "aryl". Biaryl refers to two aryl groups that are bound together by a fused ring structure as in naphthalene or connected by one or more carbon-carbon bonds as in biphenyl.

[0075] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include (but are not limited to) O, S, N, P, B, Si and Se. In many cases, O, S or N are preferred heteroatoms. Monocyclic heteroaromatic systems preferably have a single ring with 5 or 6 ring atoms, and the ring may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), wherein at least one ring is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferably, the heteroaryl is a heteroaryl containing three to thirty carbon atoms, preferably three to twenty carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthyridine, phthalazine, pteridine, dibenzopyran (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and its aza analogs. In addition, heteroaryl is optionally substituted.

[0076] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine and benzimidazole groups and their respective corresponding aza analogs are of particular interest.

[0077] The "aza" designations in the fragments described herein, i.e., azadibenzofuran, azadibenzothiophene, etc., mean that one or more CH groups in the respective aromatic rings may be replaced by nitrogen atoms, for example and without any limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0078] As used herein, the term "aldehyde" is represented by the formula -C(O)H. Throughout this specification, "C(O)" is a shorthand notation for a carbonyl group, ie, C=O.

[0079] As used herein, the term "amine" or "amino" is an amino group having the formula -NA 1 A 2 Indicates that A 1 and A 2 and X is 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 3

[0080] As used herein, the term "alkylamino" is represented by the formula -NH(-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl)amino, (tert-butyl)amino, pentylamino, isopentylamino, (tert-pentyl)amino, hexylamino, and the like.

[0081] As used herein, the term "dialkylamino" is a radical of the formula -N(-alkyl) 2 , wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, di(tert-butyl)amino, dipentylamino, diisopentylamino, di(tert-pentyl)amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

[0082] As used herein, the term "carboxylic acid" is represented by the formula -C(O)OH.

[0083] As used herein, the term "ester" is an ester of the formula -OC(O)A 1or -C(O)OA 1 Indicates that A 1 It can be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. As used herein, the term "polyester" is a polyester of the formula -(A 1 O(O)CA 2 -C(O)O) or -(A 1 O(O)CA 2 -OC(O)) a - indicates that A 1 and A 2 It may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein, and "a" is an integer from 1 to 500. "Polyester" as a term is used to describe a group produced by the reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

[0084] As used herein, the term "ether" is a 1 OA 2 Indicates that A 1 and A 2 can be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein. As used herein, the term "polyether" is a polyether having the formula -(A 1 OA 2 O) a - indicates that A 1 and A 2 It may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide and polybutylene oxide.

[0085] As used herein, the term "halo" refers to the halogens fluorine, chlorine, bromine and iodine.

[0086] As used herein, the term "heterocyclyl" refers to monocyclic and polycyclic non-aromatic ring systems and as used herein, "heteroaryl" refers to monocyclic and polycyclic aromatic ring systems: wherein at least one ring member is not carbon. The term includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole (including 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (including 1,2,4,5-tetrazine), tetrazole (including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole), thiadiazole (including 1,2,3-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole), thiazole, thiophene, triazine (including 1,3,5-triazine and 1,2,4-triazine), triazole (including 1,2,3-triazole, 1,3,4-triazole), and the like.

[0087] As used herein, the term "hydroxyl" is represented by the formula -OH.

[0088] As used herein, the term "ketone" is a compound of formula A 1 C(O)A 2 Indicates that A 1 and A 2 and alkyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.

[0089] As used herein, the term "azido" is represented by the formula -N3.

[0090] As used herein, the term "nitro" is a radical of the formula -NO 2 express.

[0091] As used herein, the term "nitrile" is represented by the formula -CN.

[0092] As used herein, the term "urea group" refers to a group of the formula -NHC(O)NH 2 Or a urea group of -NHC(O)NH-.

[0093] As used herein, the term "phosphoramide" refers to a phosphoramide of the formula -P(O)(NA 1 A 2 ) 2 A 1 and A 2 and X is 1, 2 or 3. ...

[0094] As used herein, the term "carbamyl" refers to a carboxylic acid group of the formula -CONA 1 A 2 The amide group, where A1 and A 2 and X is 1, 2 or 3. ...

[0095] As used herein, the term "sulfamoyl" refers to a radical of the formula -S(O) 2 NA 1 A 2 A 1 and A 2 and X is 1, 2 or 3. ...

[0096] As used herein, the term "silyl group" is a group having the formula -SiA 1 A 2 A 3 Indicates that A 1 , A 2 and A 3 and X is 1, 2 or 3. ...

[0097] As used herein, the term "sulfonic acid-oxo" is a radical of the formula -S(O)A 1 、-S(O) 2 A 1 、-OS(O) 2 A 1 or -OS(O) 2 OA 1 Indicates that A 1 is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. Throughout this specification, "S(O)" is a shorthand notation for S=O. The term "sulfonyl" is used herein to refer to a radical of the formula -S(O) 2 A 1 A sulfonic acid-oxy group represented by 1 is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. As used herein, the term "sulfone" is a sulfone of formula A 1 S(O) 2 A 2 Indicates that A 1 and A 2 can be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein. As used herein, the term "sulfoxide" is a sulfoxide of formula A 1 S(O)A 2 Indicates that A 1 and A 2and alkyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.

[0098] As used herein, the term "thiol" is represented by the formula -SH.

[0099] The term "polymer" includes polyalkylenes, polyethers, polyesters, and other groups having repeating units such as, but not limited to, -(CH 2 O) n -CH 3 、-(CH 2 CH 2 O) n -CH 3 、-[CH 2 CH(CH 3 )] n -CH 3 、-[CH 2 CH(COOCH 3 )] n -CH 3 、-[CH 2 CH(COOCH 2 CH 3 )] n -CH 3 and -[CH 2 CH(COO t Bu)] n -CH 3 , where n is an integer (eg, n>1 or n>2).

[0100] As used herein, "R", "R 1 ”, “R 2 ”, “R 3 ”, “R n " " (where n is an integer) may independently include hydrogen or one or more of the groups listed above. For example, if R 1 In the embodiment of the present invention, the first group is a straight chain alkyl group, wherein one hydrogen atom in the alkyl group can be optionally substituted by a hydroxyl group, an alkoxy group, an alkyl group, a halogen group, etc. According to the selected group, the first group can be incorporated into the second group, or alternatively, the first group can be side-joined (i.e., connected) to the second group. For example, for the phrase "an alkyl group comprising an amino group", the amino group can be incorporated into the main chain of the alkyl group. Alternatively, the amino group can be connected to the main chain of the alkyl group. The nature of the selected group will determine whether the first group is embedded or connected to the second group.

[0101] As used herein, the compounds of the present disclosure may contain an "optionally substituted" part. In general, the term "substituted", whether preceded by or without the term "optionally", means that one or more hydrogens in the specified part are replaced by suitable substituents. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted by more than one substituent selected from a particular group, the substituent may be the same or different at each position. The substituent combination contemplated by the present disclosure preferably can cause a stable or chemically feasible compound to form a substituent combination. It is also contemplated that in some aspects, unless explicitly stated to the contrary, a single substituent may be further optionally substituted (i.e., further substituted or unsubstituted). In some aspects, the optional substituents can be selected from the group consisting of: hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric groups and any combination thereof; wherein two or more optional substituents can be joined together to form a fused ring.

[0102] In some cases, a pair of adjacent substituents may be optionally joined or fused to form a ring. Preferred rings are five-membered, six-membered or seven-membered carbocyclic or heterocyclic rings, including two cases where a portion of the ring formed by the substituent pair is saturated and a portion of the ring formed by the substituent pair is unsaturated. As used herein, "adjacent" means that the two substituents involved can be located adjacent to each other on the same ring, or on two adjacent rings, which have two closest available positions for substitution, such as the 2,2' position in biphenyl, or the 1,8 position in naphthalene, as long as it can form a stable fused ring system.

[0103] In some aspects, the structure of the compound can be represented by the following formula:

[0104]

[0105] which is understood to be equivalent to the formula:

[0106]

[0107] where n is usually an integer. That is, R n is understood to represent five independent substituents R n(a) , R n(b), R n(c) , R n(d) , R n(e) "Independent substituents" means that each R substituent can be independently defined. For example, if R n(a) In one example, a halogen, then R n(b) Not necessarily halogen in that example.

[0108] In the chemical structures and moieties disclosed and described herein, multiple references to R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 The instructions for use of R and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Any description of R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 any structure or part thereof.

[0109] Compound

[0110] The compounds disclosed herein are suitable for a wide variety of optical and electro-optical devices, including, but not limited to, light absorbing devices, such as daylight-sensitive devices and photosensitive devices, organic light emitting devices (OLEDs), light emitting devices, or devices capable of both light absorption and light emission and as markers for biological applications.

[0111] The compounds disclosed herein are suitable for a variety of applications. As light-emitting materials, the compounds can be suitable for organic light-emitting devices (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0112] In another aspect, the compounds can provide improved efficiency, improved operating lifetime, or both in lighting devices (eg, organic light emitting devices) compared to conventional materials.

[0113] The disclosed compounds can be prepared using a variety of methods, including, but not limited to, those described in the examples provided herein.

[0114] In one aspect, the present invention relates to a compound of formula I:

[0115]

[0116] in:

[0117] M represents platinum (Pt) or palladium (Pd);

[0118] X 1 , X 2 , X 3 and X 4 Coordinated to M and independently N or C;

[0119] Cy 1 , Cy 2 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0120] Cy 3 , Cy 6 and Cy 7 is independently present or absent; wherein each Cy 3 , Cy 6 and Cy 7 are independently substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0121] Among them, when Cy 3 If it does not exist, then B 1 Selected from the group consisting of: CR 8 R 9 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 8 R 9 ,GeR 8 R 9 NR 10 , PR 10 , R 10 P=O、AsR 10 , R 10 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 10 ,BiR 10 , R 3 Bi=O、 or B 1 Does not exist and Cy 1 With Cy 2 Connect via a single button;

[0122] Among them, when Cy 3 If it exists, then B 1 Selected from the group consisting of: CR8 、SiR 8 ,GeR 8 ,N,P,P=O,As,As=O,B,R 10 Bi=O or Bi, or B 1 Does not exist and Cy 1 With Cy 2 Connect via a single button;

[0123] Among them, when Cy 6 If it does not exist, then B 2 Selected from the group consisting of: CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 11 R 12 ,GeR 11 R 12 NR 13 , PR 13 , R 13 P=O、AsR 13 , R 13 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 13 ,BiR 13 , R 13 Bi=O、 or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button;

[0124] Among them, when Cy 6 If it exists, then B 2 Selected from the group consisting of: CR 11 、SiR 11 ,GeR 11 ,N,P,P=O,As,As=O,B,R 13 Bi=O or Bi, or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button;

[0125] Among them, when Cy 7 If it does not exist, then A 4 does not exist and B 2 Yes A 8 ;

[0126] Among them, when Cy 7 If it exists, then B 2Selected by CR 14 、SiR 14 ,GeR 14 ,N,P,P=O,As,As=O,B,R 14 Bi=O or Bi;

[0127] A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of is independently absent or present, and A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of the CR 15 R 16 , CR 15 =CR 16 , C≡C, C=O, C=S, SiR 15 R 16 ,GeR 15 R 16 NR 17 , PR 17 , R 17 P=O、AsR 17 , R 17 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 17 ,BiR 17 , R 17 Bi=O、

[0128] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silane, polymeric group; or any conjugate or combination thereof;

[0129] wherein any two adjacent substituents are optionally joined to form a fused ring of Formula A, Formula B, Formula C, or Formula D:

[0130]

[0131] A 6 and A 7 Each of which is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3, R 3 Bi=O、

[0132] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Each of is independently N, C, P, O, S or Si;

[0133] Each R 7 and R 8 is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 7 and R 8 independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof; wherein any two adjacent substituents may further be joined to form a fused ring; and

[0134] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 One or more of optionally represents R X , where R X is a bulky substituent selected from the group consisting of branched alkyl, cycloalkyl, dialkylamino, diarylamino, alkylarylamino, trialkylsilyl, triarylsilyl, dialkylarylsilyl, alkyldiarylsilyl, alkylarylamino, and optionally substituted: aryl and heteroaryl.

[0135] In one embodiment, each occurrence of a bulky group is selected from the group consisting of a substituted or unsubstituted benzene ring, a heteroaryl ring, an isopropyl, a tert-butyl, or a diisopropylamino group. In one embodiment, a bulky group occurring one or more times represents a substituted aryl group. In one embodiment, a bulky group occurring one or more times represents an unsubstituted aryl group. In one embodiment, a bulky group occurring one or more times represents a fused polycyclic aryl group. In one embodiment, a bulky group occurring one or more times represents a substituted heteroaryl group. In one embodiment, a bulky group occurring one or more times represents a heteroaryl group. In one embodiment, a bulky group occurring one or more times represents a fused polycyclic heteroaryl group. In one embodiment, a bulky group occurring one or more times represents a branched alkyl group selected from the group consisting of isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, and neopentyl. In one embodiment, a bulky group occurring one or more times represents a cycloalkyl group selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and norbornyl. In one embodiment, a bulky group occurring one or more times represents a heterocycloalkyl group. In one embodiment, the bulky group occurring one or more times represents an amino group selected from the group consisting of diisopropylamino, diisobutylamino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, diisopentylamino, di(tert-pentyl)amino, N-isopropyl-N-methylamino, N-ethyl-N-isopropylamino, and N-methyl-N-(tert-butyl)amino.

[0136] In one embodiment, B 2 Existence and structure

[0137] Represents the following structure:

[0138]

[0139]

[0140] or B 2 Does not exist and Cy 6 Existence and structure Represents one of the following structures: or B 2 and Cy 6 Neither exist nor the structure

[0141] Represents one of the following structures:

[0142]

[0143]

[0144] In one embodiment, the structure

[0145]

[0146] Represents one of the following structures:

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] In one embodiment, the compound is represented by Formula II:

[0154]

[0155] in:

[0156] G 1 Yes O, NR 1 , CR 1 or S;

[0157] Y 1 , Y 2 , Y 5 , Y 6 and Y 7 are independently N, C, P, O, S or Si; and

[0158] At least one R 1 exists and represents R X .

[0159] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 1:

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] Wherein: M is platinum (Pt) or palladium (Pd);

[0166] X 1 and X 2 Each of is coordinated to M and is independently N or C;

[0167] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 Each of is independently N, C, P, O, S or Si;

[0168] Cy 1 , Cy 2 , Cy 3 , Cy 4 , Cy 5 , Cy 6 and Cy 7 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0169] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0170] B 1 , B 2 and B 3Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0171] R 庞大 Represents R X ;

[0172] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0173] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0174] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 2:

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184] in:

[0185] M is platinum (Pt) or palladium (Pd);

[0186] X 1 and X 2 Each of is coordinated to M and is independently N or C;

[0187] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 , Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 , Y 27 , Y 28 , Y 29 , Y 30 , Y 31 , Y 32 and Y 33 Each of is independently N, C, P, O, S or Si;

[0188] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0189] B 1 , B 2 and B 3 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0190] R 庞大 Represents R X ;

[0191] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0192] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0193] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 2A

[0194]

[0195]

[0196]

[0197] in:

[0198] M represents platinum (Pt) or palladium (Pd);

[0199] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 , Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 , Y 27 , Y 28 , Y 29 , Y 30 , Y 31, Y 32 , Y 33 , Y 34 and Y 35 Each of is independently C, N, P, O, S or Si;

[0200] A 1 and A 2 Each of A is independently non-existent or existent, and the existent A 1 and A 2 Each of the CR 15 R 16 , CR 15 =CR 16 , C≡C, C=O, C=S, SiR 15 R 16 ,GeR 15 R 16 NR 17 , PR 17 , R 17 P=O、AsR 17 , R 17 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 17 ,BiR 17 , R 17 Bi=O、

[0201] R 庞大 Represents R X ;

[0202] When the valence permits, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 Each of R is independently absent or present, and each R that exists 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, arylalkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof.

[0203] R on the same ring or adjacent rings 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 Any two of are optionally bonded together to form a fused ring system of Formula A, Formula B, Formula C, or Formula D.

[0204] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 3:

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] in:

[0215] M is platinum (Pt) or palladium (Pd);

[0216] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 and Y 13 Each of is independently N, C, P, O, S or Si;

[0217] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0218] B 1 , B 2 and B 3 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0219] R 庞大 Represents R X ;

[0220] R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0221] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0222] In one embodiment, the compound is represented by Formula III:

[0223]

[0224] in:

[0225] Y 5 , Y 6 and Y 7 Each of is independently N, C, P, O, S or Si;

[0226] Cy 1 is selected from the group consisting of N-heterocyclic carbenes, carbenes, imidazoles and benzimidazoles; wherein when Cy 1 When it is N-heterocyclic carbene or carbene, X 1 is C and Y 8 is N; and when Cy 1 When it is imidazole or benzimidazole, X 1 is N and Y 8 It is C.

[0227] X 1 is N; and

[0228] Y 5 Optionally with R 1or R 1 The substituents on the amine are fused to form a ring.

[0229] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 4:

[0230]

[0231]

[0232]

[0233]

[0234] in:

[0235] M is platinum (Pt) or palladium (Pd);

[0236] Cy 1 , Cy 2 , Cy 3 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0237] A 1 , A 2 and A 3 Each of the above is independently non-existent or existent; 1 , A 2 and A 3 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0238]

[0239] Y1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 and Y 20 Each of is independently N, C, P, O, S or Si;

[0240] Each Ar is independently substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl or heterocyclyl;

[0241] B 1 and B 2 Each of which is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 or R 3 Bi=O;

[0242] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0243] Wherein any two substituents are optionally joined to form a ring, the ring is optionally further substituted.

[0244] In one embodiment, part

[0245]

[0246] Independently is one of the following structures:

[0247]

[0248] in:

[0249] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 and Y 10 Each of is independently N, C, P, O, S or Si;

[0250] R 1 , R 2 , R 3 , R 4 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, arylalkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof.

[0251] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 5:

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265] in:

[0266] M is platinum (Pt) or palladium (Pd);

[0267] Cy 1 , Cy 2 and Cy 3 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0268] A 1 , A2 and A 3 Each of which is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O;

[0269] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 , Y 20 Each of is independently N, C, P, O, S or Si;

[0270] Ar is independently substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl;

[0271] B 1 , B 2 and A 1 Each is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,

[0272] G JZ 1 R2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 ,

[0273] BR 3 ,BiR 3 , R 3 Bi=O;

[0274] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0275] The condition is R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of the X ;

[0276] wherein any two adjacent substituents are optionally joined to form a fused ring of Formula A, Formula B, Formula C, or Formula D.

[0277] In one embodiment, Cy 1 represents N-heterocyclic carbene;

[0278] X 1 represents C; and

[0279] Two groups R 1 joined to form a ring, the ring further being formed by at least one R X replace; or

[0280] Two groups R 1 to form a ring, which is connected by a divalent linking group A X Substitution, where A X Covalently bonded to Cy 2 ; and A X Indicates single key, CR 15 R 16 , CR 15 =CR 16 , C≡C, C=O, C=S, SiR 15 R 16 ,GeR 15 R 16 NR 17 , PR 17 , R 17 P=O、AsR 17 , R 17 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 17 ,BiR 17 , R 17 Bi=O、

[0281] In one embodiment, Cy 1 represents N-heterocyclic carbene;

[0282] X 1 represents C; and

[0283] Two adjacent substituents R 3 are present and taken together represent a group of formula C.

[0284] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 6:

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] in:

[0291] M is platinum (Pt) or palladium (Pd);

[0292] X 1 and X 2 Each of is coordinated to M and is independently N or C;

[0293] Y 1a , Y 1b , Y 1c , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 Each of is independently N, C, P, O, S or Si;

[0294] Cy 1 , Cy 2 , Cy 3 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0295] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R3 Bi=O、

[0296] B 1 and B 2 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0297] R 庞大 Represents R X ;

[0298] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0299] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0300] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 7:

[0301]

[0302]

[0303]

[0304]

[0305]

[0306] Wherein: M is platinum (Pt) or palladium (Pd);

[0307] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 and Y 15 Each of is independently N, C, P, O, S or Si;

[0308] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0309] B 1 , B 2 and B 3 Each of which is independently CR 1 、SiR 1 ,GeR1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0310] R 庞大 Represents R X ;

[0311] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0312] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0313] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 7A:

[0314]

[0315]

[0316]

[0317] in:

[0318] Each Y 1a , Y 1b , Y 1c , Y 1 , Y 2 , Y 3 , Y 4 , Y5 , Y 6 and Y 7 are independently N, C, P, O, S or Si;

[0319] A 1 is non-existent or exists; if it exists, then A 1 Indicates single key, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0320] R 庞大 Represents R X ;

[0321] R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 and R 19 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silane, polymeric group; or any conjugate or combination thereof;

[0322] wherein any two adjacent substituents are optionally joined to form a ring, which is optionally further substituted;

[0323] U stands for CR 1 R 2 、C=O、C=S、SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、

[0324] O, S, S=O, SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0325] In one embodiment, A 1 Does not exist; Cy 1 is a heteroaryl group; X 1 is N; and two adjacent substituents R 1 , two adjacent substituents R 2 , two adjacent substituents R 3 or two adjacent substituents R 7are present and taken together represent a group of formula C.

[0326] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 8:

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367] in:

[0368] M represents platinum (Pt) or palladium (Pd);

[0369] X 1 and X 2 Each of is coordinated to M and is independently N or C;

[0370] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 , Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 and Y 27 Each of is independently N, C, P, O, S or Si;

[0371] Cy 1 , Cy 2 , Cy 3 and Cy 4 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0372] A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0373] B 1 and B 2 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0374] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0375] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0376] In one embodiment, B 1 Does not exist; B 2 Does not exist; Cy 1 is a heteroaryl group; X 1 is N; and

[0377] structure express

[0378] wherein R' and R" independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric groups, or any conjugates or combinations thereof; and each occurrence of R" represents aryl or heteroaryl;

[0379] Wherein any two adjacent groups R' or R" are optionally joined to form a fused ring, which is optionally further substituted.

[0380] In one embodiment, B 1 Does not exist; Cy 1 is a heteroaryl group; X 1 is N; and two adjacent substituents R 1 , two adjacent substituents R 2 , two adjacent substituents R 3 or two adjacent substituents R 7 are present and taken together represent a group of formula C.

[0381] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 9:

[0382]

[0383]

[0384]

[0385] in:

[0386] M is platinum (Pt) or palladium (Pd);

[0387] X 1 and X 2 Each of is coordinated to M and is independently N or C;

[0388] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 Each of is independently N, C, P, O, S or Si;

[0389] Cy 1 , Cy 2 , Cy 3 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene;

[0390] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0391] B 1 and B 2 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0392] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R4 , R 5 and R 6 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0393] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0394] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 10:

[0395]

[0396]

[0397]

[0398] Wherein: M is platinum (Pt) or palladium (Pd);

[0399] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 and Y 15 Each of is independently N, C, P, O, S or Si;

[0400] A 1 , A 2 , A 3 and A 4 Each of the above is independently non-existent or existent; 1 , A 2 , A 3 and A 4 Each of the CR 1 R 2, CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O、O、S、S=O、SO 2 ,Se,Se=O,SeO 2 , BR 3 ,BiR 3 , R 3 Bi=O、

[0401] B 1 and B 2 Each of which is independently CR 1 、SiR 1 ,GeR 1 ,N,P,P=O,As,As=O,B,R 3 Bi=O or Bi;

[0402] R 庞大 Represents R X ;

[0403] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof;

[0404] Wherein any two adjacent substituents are optionally joined to form a ring, said ring is optionally further substituted.

[0405] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 11:

[0406]

[0407]

[0408]

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418]

[0419]

[0420]

[0421]

[0422]

[0423]

[0424]

[0425]

[0426]

[0427]

[0428]

[0429]

[0430]

[0431]

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443]

[0444]

[0445]

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454]

[0455]

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

[0462]

[0463]

[0464] wherein each occurrence of R is methyl, isopropyl, tert-butyl, phenyl, and the like;

[0465] Each occurrence of R' is methyl, isopropyl, tert-butyl, and their analogs;

[0466]

[0467] X is O, S, NR 1 、Si(R 1 )R 2 , C(R 1 )R 2 , and the like; and Y is O, S, NR 1 、Si(R 1 )R 2 , C(R 1 )R 2 , and its analogs.

[0468] In one embodiment, the compound is represented by one of the following structures, which together represent Listing 11A:

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482] Compositions and devices of the present invention

[0483] Also disclosed herein are organic light emitting diodes or light emitting devices comprising one or more compounds and / or compositions disclosed herein.

[0484] In one embodiment, the device comprises an anode; a cathode; and an organic layer, at least one of the organic layers disposed between the anode and the cathode and comprising at least one compound disclosed herein.

[0485] In one embodiment, the device comprises a first emitting layer containing one or more phosphorescent or fluorescent emitters and a second emitting layer containing one or more phosphorescent or fluorescent emitters; wherein the first emitting layer is disposed between an anode and the second emitting layer; and wherein the second emitting layer is disposed between the first emitting layer and a cathode.

[0486] In one aspect, the device is an electro-optical device. Electro-optical devices include, but are not limited to, light absorbing devices, such as daylight sensitive devices and photosensitive devices, organic light emitting devices, light emitting devices, or devices capable of absorbing and emitting and serving as markers for biological applications. For example, the device can be an OLED.

[0487] OLEDs utilize organic thin films that emit light when voltage is applied to the device. OLEDs are becoming an increasingly attractive technology for applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0488] In general, an OLED comprises at least one organic layer disposed between an anode and a cathode and electrically connected to the anode and the cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into one or more organic layers. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes via a photoemission mechanism, light is emitted. The exciton can be localized on an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0489] The original OLEDs utilized emissive molecules to emit light from their singlet states ("fluorescence"), as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0490] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. The following references are incorporated herein by reference in their entirety: Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, Nos. 3, 4-6 (1999) ("Baldo-II"). Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, Col. 5-6, which is incorporated by reference.

[0491] One application of phosphorescent emitting molecules is full color displays. Industry standards for such displays require pixels adapted to emit specific colors (referred to as "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates, which are well known in the art. Such devices are disclosed herein, comprising one or more compounds or compositions disclosed herein.

[0492] In one embodiment, the device is a white OLED. In one embodiment, the device emits amber light and blue light, which when combined are received as white light. In one embodiment, the color (ie, warmth) of the white light can be adjusted by varying the thickness and concentration of the various emissive layers.

[0493] OLEDs can be manufactured by methods known to those skilled in the art. In general, OLEDs are manufactured by continuous vapor deposition of individual layers onto a suitable substrate. Suitable substrates include, for example, glass, inorganic materials (e.g., ITO or IZO), or polymer films. For vapor deposition, conventional techniques such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD), etc. can be used.

[0494] In an alternative process, the organic layer can be applied from a solution or dispersion in a suitable solvent, in which case coating techniques known to those skilled in the art are used. Suitable coating techniques are, for example, spin coating, casting, Langmuir-Blodgett ("LB"), inkjet printing, dip coating, relief printing, screen printing, doctor blade printing, slot coating, roller printing, reverse roller printing, lithography, flexography, rotary printing, spraying, brushing or pad printing, etc. Among the processes mentioned, in addition to the aforementioned vapor deposition, spin coating, inkjet printing and casting are preferred because they are particularly simple and inexpensive to perform. In the case where the layers of the OLED are obtained by spin coating, casting or inkjet printing, the coating can be obtained using a solution prepared by dissolving the composition in a concentration of 0.0001 to 90% by weight in a suitable organic solvent (e.g., benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof).

[0495] The compounds described herein can be used in light emitting devices, such as OLEDs. Figure 1 A cross-sectional view of an OLED 100 is depicted. The OLED 100 includes a substrate 102, an anode 104, a hole transport material (HTL) 106, a light management material 108, an electron transport material (ETL) 110, and a metal cathode layer 112. The anode 104 is typically a transparent material such as indium tin oxide. The light management material 108 may be an emitting material (EML) including an emitter and a host.

[0496] In many aspects, Figure 1Any of the one or more layers depicted may include indium tin oxide (ITO), poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), N,N'-di-1-naphthyl-N,N-diphenyl-1,1'-biphenyl-4,4'-diamine (NPD), 1,1-bis((di-4-methylphenylamino)phenyl)cyclohexane (TAPC), 2,6-bis(N-carbazolyl)pyridine (mCpy), 2,8-bis(diphenylphosphoryl)dibenzothiophene (PO15), LiF, Al, or a combination thereof.

[0497] The light treatment material 108 may include one or more compounds of the present disclosure, optionally together with a host material. The host material may be any suitable host material known in the art. The emission color of the OLED is determined by the emission energy (optical bandgap) of the light treatment material 108, and the emission color can be adjusted by adjusting the electronic structure of the emission compound, the host material, or both. The hole transport material in the HTL layer 106 and the electron transport material in the ETL layer 110 may include any suitable hole transporter known in the art.

[0498] The compounds described herein can exhibit phosphorescence. The device efficiency of phosphorescent OLEDs (i.e., OLEDs having phosphorescent emitters) is generally higher than the device efficiency of other OLEDs (such as fluorescent OLEDs). Light-emitting devices based on electrophosphorescent emitters are described in more detail in WO 2000 / 070655 to Baldo et al., which is incorporated herein by reference for its teachings on OLEDs, and in particular phosphorescent OLEDs.

[0499] As contemplated herein, the OLED of the present invention may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer may include a compound of the present invention and variations thereof as described herein.

[0500] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0501] In some embodiments, the OLED further comprises a layer containing a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0502] In one embodiment, the consumer product is selected from the group consisting of: a flat panel display, a computer monitor, a medical monitor, a television, a sign, a light for interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a phone, a cell phone, a tablet computer, a tablet phone, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay (less than 2 inches diagonal), a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and a sign.

[0503] In some embodiments of the emission region, the emission region further comprises a body, wherein the body comprises at least one selected from the group consisting of: a metal complex, a triphenylene, a carbazole, a dibenzothiophene, a dibenzofuran, a dibenzoselenophene, an aza-triphenylene, an aza-carbazole, an aza-dibenzothiophene, an aza-dibenzofuran, and an aza-dibenzoselenophene.

[0504] The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) bipolar, b) electron transport, c) hole transport, or d) wide bandgap material that has little charge transport effect. In some embodiments, the host may include a metal complex. The host may be a triphenylene containing benzofused thiophene or benzofused furan. Any substituent in the host may be a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 ,OAr 1 、N(C n H 2n+1 ) 2 、N(Ar 1 )(Ar 2 ), CH=CH-C n H 2n+1 、C≡CCn H 2n+1 ,Ar 1 ,Ar 1 -Ar 2 and C n H 2n -Ar 1 , or the subject has no substitution. In the aforementioned substituents, n may be in the range of 1 to 10; and Ar 1 and Ar 2 The host may be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and heteroaromatic analogs thereof. The host may be an inorganic compound. For example, a Zn-containing inorganic material, such as ZnS.

[0505] Suitable hosts may include, but are not limited to, mCP (1,3-bis(carbazol-9-yl)benzene), mCPy (2,6-bis(N-carbazol-9-yl)pyridine), TCP (1,3,5-tris(carbazol-9-yl)benzene), TCTA (4,4',4"-tri(carbazol-9-yl)triphenylamine), TPBi (1,3,5-tri(1-phenyl-1-H-benzimidazol-2-yl)benzene), mCBP (3,3-bis(9H-carbazol-9-yl)biphenyl), pCBP (4,4'-bis(carbazol-9-yl)biphenyl), CDBP (4,4'-bis(9-carbazol-9-yl)-2,2'-dimethylbiphenyl), DMFL-CBP (4,4'-bis(carbazol-9-yl)-9,9-dimethylfluorene), FL-4CBP (4,4'-bis(carbazol-9-yl)-9,9-bis(9-phenyl-9H-carbazol)fluorene), FL-2CBP (9,9-bis( 4-carbazol-9-yl)phenyl)fluorene (also abbreviated as CPF), DPFL-CBP (4,4'-bis(carbazol-9-yl)-9,9-dimethylphenylfluorene), FL-2CBP (9,9-bis(9-phenyl-9H-carbazol)fluorene), spiroCBP (2,2',7,7'-tetra(carbazol-9-yl)-9,9'-spirobifluorene), ADN (9,10-di(naphthalene-2-yl)anthracene), TBADN (3-tert-butyl-9,10-di(naphthalene-2-yl)anthracene), DPVBi (4,4'-bis(2,2-diphenylethylene-1-yl)-4,4'-dimethylphenyl), p-DMDPVBi (4,4'-bis(2, 2-Diphenylethylene-1-yl)-4,4'-dimethylphenyl), TDAF (tert-(9,9-diarylfluorene)), BSBF (2-(9,9'-spirobifluorene-2-yl)-9,9'-spirobifluorene), TSBF (2,7-bis(9,9'-spirobifluorene-2-yl)-9,9'-spirobifluorene), BDAF (bis(9,9-diarylfluorene)), p-TDPVBi (4,4'-bis(2,2-diphenylethylene-1-yl)-4,4'-di-(tert-butyl)phenyl), TPB3 (1,3,5-tri(pyrene-1-yl)benzene, PBD (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4 -oxadiazole), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthene), BP-OXD-Bpy (6,6'-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazol-2-yl]-2,2'-bipyridyl), NTAZ (4-(naphthalene-1-yl)-3,5-diphenyl-4H-1,2,4-triazole), Bpy-OXD (1,3-bis[2-(2,2'-bipyridyl-6-yl)-1,3,4-oxadiazol-5-yl]benzene), BPhen (4,7-diphenyl-1,10-phenanthene), TAZ (3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole), PADN (2-phenyl-9,10-di(naphthalene-2-yl)anthracene), Bpy-FOXD (2,7-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazol-5-yl]-9,9-dimethylfluorene), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazol-5-yl]benzene), HNBphen (2-(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthracene), NBphen (2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthene), 3TPYMB (tri(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane), 2-NPIP (1-methyl-2-(4-(naphthalene-2-yl)phenyl)-1H-imidazo[4,5-f]-[1,10]phenanthene), Liq (8-hydroxyquinoline lithium), and Alq (bis(2-methyl-8-quinoline)-4-(phenylphenol)aluminum), and mixtures thereof. ,

[0506] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also referred to as supermolecules). As used herein, "monovalent variants of a compound" refers to a portion that is identical to the compound, but one hydrogen has been removed and replaced by a bond to the rest of the chemical structure. As used herein, "multivalent variants of a compound" refers to a portion that is identical to the compound, but more than one hydrogen has been removed and replaced by one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds.

[0507] The materials described herein as being suitable for use in a particular layer in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the light-emitting dopants disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0508] The charge transport layer can be doped with a conductivity dopant to substantially change its charge carrier density and, in turn, its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and, depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

[0509] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified in the references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0510] The hole injection / transport material used in the present invention is not particularly limited, and any compound can be used as long as the compound is typically used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0511] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in the device can result in significantly improved efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0512] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used together with any dopant as long as the triplet criterion is satisfied.

[0513] Emitter examples are not particularly limited, and any compound can be used as long as the compound is typically used as an emitter material. Suitable emitter material examples include, but are not limited to, compounds capable of generating emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF (also known as E-type delayed fluorescence; see, e.g., U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety)), triplet-triplet annihilation, metal-assisted delayed fluorescence (MADF), or a combination of these processes. In some embodiments, the emissive dopant may be a racemic mixture, or may be enriched in one enantiomer.

[0514] One or more other emitter dopants may be used in combination with the compounds of the present disclosure. 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.

[0515] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of the blocking layer in the device can produce substantially higher efficiency and / or longer lifetime than a similar device lacking the blocking layer. In addition, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than one or more hosts closest to the HBL interface.

[0516] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal composite or organic compound may be used as long as it is typically used to transport electrons.

[0517] In tandem or stacked OLEDs, CGL plays an important role in performance and consists of n-type and p-type doped layers for injecting electrons and holes, respectively. Electrons and holes are supplied by CGL and electrodes. Electrons and holes consumed in CGL are refilled by electrons and holes injected from cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in transport layers.

[0518] In any of the above compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specific listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0519] In yet another aspect of the present disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, and an electron transport layer material.

[0520] Experimental Examples

[0521] The present invention is further described in detail with reference to the following experimental examples. Unless otherwise stated, these examples are provided for the purpose of illustration only and not for the purpose of limitation. Therefore, the present invention should never be interpreted as being limited to the following examples, but should be interpreted as covering any and all changes that become apparent due to the teachings provided herein.

[0522] Without further description, it is believed that one of ordinary skill in the art can use the foregoing description and the following illustrative examples to make and utilize the composite materials of the present invention and to practice the claimed methods. Therefore, the following working examples particularly point out preferred embodiments of the present invention and should not be construed as limiting the remainder of the disclosure in any way.

[0523] Example 1: Tetradentate platinum and palladium complex emitters using benzocarbenes with bulky substituents and their analogs

[0524] OLED (Organic Light Emitting Diode) is a planar light emitting technology consisting of a series of organic thin films between two conductors. When electricity is applied through adjacent electrodes, bright light is emitted. OLED displays have found their way into many handheld products since their inception and continue to be popular in the mobile market. The OLED field has seen consistent growth with the steady introduction of production improvements and new material design strategies. Although great progress has been made in this field, there are still many challenges, in particular, the development of stable, narrow and efficient blue emitters remains a considerable shortfall for continued efforts in the field of organic displays and lighting. In the present invention, a series of platinum (II) and palladium (II) complexes have been designed, which have bulky substituents based on benzocarbenes and their analogs. Such emitters can be used for full-color displays and lighting applications.

[0525] The phosphorescence spectra of the exemplary compounds are shown in Figure 2 , 3 and 4 in.

[0526] Tetradentate Pt complexes are potential emitter candidates for display applications. However, PtON5-dtb exhibits significantly enhanced emission vibronic sidebands at room temperature compared to the 77K emission spectrum ( Figure 5 ), which can be attributed to T 1 State and T 1 *state( Figure 6 ) are potentially mixed at room temperature. Therefore, in order to increase T 1 State and T 1 * states and suppress the emission of electronic vibration sidebands, hoping that T 1 * Stable state or T 1 The state is stable. Figure 2 Such molecular design principles are illustrated in , which propose to narrow the emission spectrum of the Pt complex by generating intramolecular interactions between the phenyl group and the benzimidazole-carbene group, between the benzimidazole-carbene group and the carbene-bonded aryl group, and between the carbene-bonded aryl group and the pyridyl group. 1 * state is unstable or by extending the conjugation level of the carbazole group to make T 1 To achieve state stability ( Figure 7 ).

[0527] In addition, the emitter and the host (for example, the electron-rich carbazole group from SiTrzCz2 and the electron-deficient benzimidazole carbene group from PtON5-m) Figure 8 ))'s random intramolecular interactions cause the emission spectrum to red-shift ( Figure 5), which can impair the color quality of blue phosphorescent OLEDs and affect the operational stability of the device at different levels of host-emitter interaction. Therefore, it is also desirable to suppress such intramolecular interactions between the Pt complex and the host material by adding bulky groups to the phenylbenzimidazole-carbene group. As an additional benefit, the emission peak of PtON5-m in the SiTrzCz2 film ( Fig. 9 ) compared to the emission peak of PtON5-dtb-m in SiTrzCz2 film ( Fig.10 )blue shift 2nm.

[0528] Other phosphorescence spectra of exemplary compounds are shown in Fig.11 , 12 and 13 in.

[0529] The compounds of the present invention are prepared by the following method:

[0530] Ex.1

[0531]

[0532] Ex.2

[0533]

[0534] Ex.3

[0535]

[0536] Ex.4

[0537]

[0538] Ex.5

[0539]

[0540] Ex.6

[0541]

[0542] Ex.7

[0543]

[0544] Ex.8

[0545]

[0546] Ex.9

[0547]

[0548] Ex.10

[0549]

[0550] Ex.11

[0551]

[0552] Ex.12

[0553]

[0554] Ex.13

[0555]

[0556] Ex.14

[0557]

[0558] Ex.15

[0559]

[0560] Ex.16

[0561]

[0562] Ex.17

[0563]

[0564] Ex.18

[0565]

[0566] Ex.1-1:

[0567]

[0568] Ex.1-2:

[0569]

[0570] Ex.1-3:

[0571]

[0572] Ex.1-4:

[0573]

[0574] Ex.1-5:

[0575]

[0576] Ex.1-6:

[0577]

[0578] Ex.1-7:

[0579]

[0580] Ex.1-8:

[0581]

[0582] Ex.1-9:

[0583]

[0584] Ex.1-10:

[0585]

[0586] Ex.1-11:

[0587]

[0588] Ex.1-12:

[0589]

[0590] Ex.1-13:

[0591]

[0592] Ex.1-14:

[0593]

[0594] Ex.1-15:

[0595]

[0596] Ex.1-16:

[0597]

[0598] Ex.1-17:

[0599]

[0600] Ex.1-18:

[0601]

[0602] Ex.1-19:

[0603]

[0604] Ex.1-20:

[0605]

[0606] Ex.1-21:

[0607]

[0608] Ex.1-22:

[0609]

[0610] Ex.1-23:

[0611]

[0612] Ex.1-24:

[0613]

[0614] Ex.1-25:

[0615]

[0616] Ex.1-26:

[0617]

[0618] Ex.1-27:

[0619]

[0620] Ex.1-28:

[0621]

[0622] Ex.1-29:

[0623]

[0624] Ex.1-30:

[0625]

[0626] Ex.1-31:

[0627]

[0628] Ex.1-32:

[0629]

[0630] Ex.1-33:

[0631]

[0632] Ex.1-34:

[0633]

[0634] Ex.1-35:

[0635]

[0636] Ex.1-36:

[0637]

[0638] Example 2: Tetradentate Metal Complex Emitters Based on Functionalized Imidazolyl Groups and Their Analogs

[0639] Metal complexes using functionalized imidazolyl groups and their analogs have been designed. In this innovation, a series of novel tetradentate platinum (II) and palladium (II) complexes have been developed that incorporate functionalized imidazolyl groups and their analogs. This class of these emitters has potential applications in full-color displays and lighting. This class of emitters can be used in full-color display and lighting applications.

[0640] The photoluminescence spectra of exemplary compounds are presented in Fig.14 , 15 and 16 in.

[0641] These compounds can be synthesized by:

[0642] Ex.1

[0643]

[0644] Preparation of 1-2: To a solution of 1-1 in acetic acid (0.1 M) was added aqueous HBr (48 wt %, 10 eq.). The mixture was heated in a 120° C. oil bath for 12 hours. The mixture was cooled to room temperature and then water (equal to the volume of acetic acid) was added. The mixture was treated with solid K 2 CO 3 Neutralize to pH 5-6. The precipitate is collected by filtration, washed 3 times with water and dried under reduced pressure. The yield is quantitative.

[0645] Preparation of 1-4: To a solution of 1-2 (1 eq) in DMSO (0.1 M) were added 1-3 (1.2 eq), Cul (0.1 eq), 2-picolinic acid (0.2 eq) and K 3 PO 4 (2eq). The reaction mixture was heated to reflux for 24 hours. The mixture was cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted 3 times with EtOAc. The combined organic phases were then concentrated. Purification by column chromatography (hexane: EtOAc = 8:1 to 3:1) gave 1-4.

[0646] Preparation of 1-6: Add 1-4 (1 eq), 1-5 (1.1 eq), Pd 2 (dba) 3 In the mixture of 4-nitro-2-nitropropene (0.1 eq), 4-nitro-2-nitropropene (0.2 eq), ...). The flask was then evacuated and backfilled 3 times with nitrogen, toluene (0.1 M) was subsequently added via a syringe. The mixture was heated to reflux and maintained for 12 hours. The mixture was cooled to room temperature, and the product was isolated by column chromatography (hexane: EtOAc 5:1 to 3:1), 85% yield.

[0647] Preparation of 1-7: Reaction of 1-6 with CH(OEt) 3 To the solution in (50 eq) was added aqueous HCl (aq) (37 wt%, 5 eq). The mixture was heated in a 100°C oil bath for 12 hours. The mixture was cooled to room temperature and then water (volume equal to HCl (aq.)) was added. The mixture was washed with solid K 2 CO 3 Neutralized to pH 7-8. The precipitate was collected by filtration, rinsed 3 times with water and dried under reduced pressure. Product 1-7 was isolated by column chromatography (DCM:MeOH 25:1 to 15:1) in 81% yield.

[0648] Preparation of 1-8: Resuspend 1-7 in MeOH / H 2 Add NH 4 PF 6 (2 eq). The mixture was stirred at room temperature for 12 hours. The precipitate was collected by filtration, rinsed 3 times with water and dried under reduced pressure. The yield was quantitative.

[0649] Preparation of 1-9: To a solution of 1-8 (1 eq) in 1,4-dioxane (0.2 M) was added Pt(COD)Cl 2 (1.1 eq) and NaOAc (2 eq). The mixture was heated to reflux for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. Purification by column chromatography (hexane: DCM = 1: 2 to 1: 3) gave 1-9 in 48% yield.

[0650] Ex.2

[0651]

[0652] program:

[0653] Preparation of 2-3: Add 2-1 (1.1 eq), 2-2 (1 eq) and Pd(PPh 3 ) 4(0.05 eq). The flask was then evacuated and backfilled with nitrogen three times. K 3 PO 4 Aqueous solution (2M, 3eq) and 1,4-dioxane (0.2M). The mixture was heated in a 100°C oil bath for about 10 hours. The mixture was cooled to room temperature and the product was isolated by column chromatography (hexane: EtOAc = 5:1 to 1:1), 80% yield.

[0654] Preparation of 2-3: To a solution of 2-3 (1 eq) in DMSO (0.1 M) was added 2-4 (1.2 eq). The reaction mixture was heated to 130 ° C for 24 hours. The mixture was cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted 3 times with EtOAc. The combined organic phases were then concentrated. Purification by column chromatography (hexane: EtOAc = 8: 1 to 3: 1) gave 2-5.

[0655] Preparation of 2-6: To a solution of 2-5 in acetic acid (0.1 M) was added aqueous HBr (48 wt %, 10 eq.). The mixture was heated in a 120° C. oil bath for 12 hours. The mixture was cooled to room temperature and then water (equal to the volume of acetic acid) was added. The mixture was treated with solid K 2 CO 3 Neutralize to pH 5-6. The precipitate is collected by filtration, washed 3 times with water and dried under reduced pressure. The yield is quantitative.

[0656] Preparation of 2-7: To a solution of 2-6 (1 eq) in DMSO (0.1 M) were added 1-3 (1.2 eq), Cul (0.1 eq), 2-picolinic acid (0.2 eq) and K 3 PO 4 (2eq). The reaction mixture was heated to reflux for 24 hours. The mixture was cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted 3 times with EtOAc. The combined organic phases were then concentrated. Purification by column chromatography (hexane: EtOAc = 8: 1 to 3: 1) gave 2-7.

[0657] Preparation of 2-8: Add 2-7 (1 eq), 1-5 (1.1 eq), Pd 2 (dba) 3 In the mixture of 4-nitro-2-nitropropene (0.1 eq), 4-nitro-2-nitropropene (0.2 eq), ...). The flask was then evacuated and backfilled 3 times with nitrogen, toluene (0.1 M) was subsequently added via a syringe. The mixture was heated to reflux and maintained for 12 hours. The mixture was cooled to room temperature, and the product was isolated by column chromatography (hexane: EtOAc 5:1 to 3:1), 85% yield.

[0658] Preparation of 2-9: Reverse the reaction mixture of 2-8 and CH(OEt) 3 To the solution in (50 eq) was added aqueous HCl (aq) (37 wt%, 5 eq). The mixture was heated in a 100°C oil bath for 12 hours. The mixture was cooled to room temperature and then water (volume equal to HCl (aq.)) was added. The mixture was washed with solid K 2 CO 3 Neutralized to pH 7-8. The precipitate was collected by filtration, rinsed 3 times with water and dried under reduced pressure. The product 2-9 was isolated by column chromatography (DCM:MeOH 25:1 to 15:1) in 81% yield.

[0659] Preparation of 2-10: Prepare 2-9 in MeOH / H 2 Add NH 4 PF 6 (2 eq). The mixture was stirred at room temperature for 12 hours. The precipitate was collected by filtration, rinsed 3 times with water and dried under reduced pressure. The yield was quantitative.

[0660] Preparation of 2-11: To a solution of 2-10 (1 eq) in 1,4-dioxane (0.2 M) was added Pt(COD)Cl 2 (1.1 eq) and NaOAc (2 eq). The mixture was heated to reflux for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. Purification by column chromatography (hexane: DCM = 1: 2 to 1: 3) gave 2-11 in 48% yield.

[0661] Ex.3

[0662]

[0663] Preparation of 3-3: To a solution of 3-1 (1 eq) in DMSO (0.1 M) were added 3-2 (1.2 eq), Cul (0.1 eq), 2-picolinic acid (0.2 eq) and K 3 PO 4 (2eq). The reaction mixture was heated to reflux for 24 hours. The mixture was cooled to room temperature. Water (3 times the volume of DMSO) was then added. The mixture was extracted 3 times with EtOAc. The combined organic phases were then concentrated. 3-3 was obtained by column chromatography (hexane: EtOAc = 3: 1 to 1: 1).

[0664] Preparation of 3-4: To a solution of 3-3 (1 eq) in HOAc (0.2 M) was added K 2 PtCl 4(1.1 eq) and TBAB (0.2 eq). The mixture was heated to reflux for 3 days. The reaction mixture was cooled to room temperature and filtered through a short silica gel pad. The filtrate was concentrated under reduced pressure. Purification by column chromatography (hexane: DCM = 1: 2 to 1: 3) gave 3-4 in 52% yield.

[0665] Ex.4

[0666]

[0667] Ex.5

[0668]

[0669] Ex.6

[0670]

[0671] Example 3: Tetradentate platinum and palladium complex emitters with narrow emission spectra that can be synthesized by phenyl-benzoic acid based Rigid structural design of carbene and its analogs

[0672] In the present invention, a series of tetradentate platinum and palladium complexes have been designed, which can be realized through a rigid structural design based on phenyl-benzocarbene and its analogs. Such emitters can be used in full-color display and lighting applications.

[0673] The PL spectra of the exemplary compounds are shown in Fig.18 middle.

[0674] The compounds of the present invention can be synthesized by the following method: Ex.1

[0675]

[0676] Ex.2

[0677]

[0678] Ex.3

[0679]

[0680] Ex.4

[0681]

[0682] Ex.5

[0683]

[0684] Ex.6

[0685]

[0686] Ex.7

[0687]

[0688] Ex.8

[0689]

[0690] Ex.9

[0691]

[0692] Ex.10

[0693]

[0694] Ex.11

[0695]

[0696] Ex.3-1:

[0697]

[0698] Ex.3-2:

[0699]

[0700] Ex.3-3:

[0701]

[0702] Ex.3-4:

[0703]

[0704] Ex.3-5:

[0705]

[0706] Ex.3-6:

[0707]

[0708] Ex.3-7:

[0709]

[0710] Ex.3-8:

[0711]

[0712] Ex.3-9:

[0713]

[0714] Ex.3-10:

[0715]

[0716] Ex.3-11:

[0717]

[0718] Ex.3-12:

[0719]

[0720] Ex.3-13:

[0721]

[0722] Ex.3-14:

[0723]

[0724] Ex.3-15:

[0725]

[0726] Ex.3-16:

[0727]

[0728] Ex.3-17:

[0729]

[0730] Ex.3-18:

[0731]

[0732] Ex.3-19:

[0733]

[0734] Ex.3-20:

[0735]

[0736] Ex.3-21:

[0737]

[0738] Ex.3-22:

[0739]

[0740] Ex.3-23 and 24:

[0741]

[0742] Ex.3-25:

[0743]

[0744] Ex.3-26 and 27:

[0745]

[0746] Ex.3-28:

[0747]

[0748] Ex.3-29 and 30:

[0749]

[0750] Ex.3-31:

[0751]

[0752] Ex.3-32 and 33:

[0753]

[0754] Ex.3-34:

[0755]

[0756] Ex.3-35 and 36:

[0757]

[0758] Ex.3-37:

[0759]

[0760] Ex.3-38 and 39:

[0761]

[0762] Ex.3-40:

[0763]

[0764] Ex.3-41 and 42:

[0765]

[0766] Ex.3-43:

[0767]

[0768] Ex.3-44 and 45:

[0769]

[0770] Ex.3-46:

[0771]

[0772] Ex.3-47 and 48:

[0773]

[0774] Ex.3-49:

[0775]

[0776] Ex.3-50 and 51:

[0777]

[0778] Ex.3-52:

[0779]

[0780] Ex.3-53 and 54:

[0781]

[0782] Ex.3-55:

[0783]

[0784] Ex.3-56 and 57:

[0785]

[0786] Ex.3-58:

[0787]

[0788] Ex.3-59 and 60:

[0789]

[0790] Ex.3-61:

[0791]

[0792] Ex.3-62 and 63:

[0793]

[0794] Ex.3-64:

[0795]

[0796] Ex.3-65 and 66:

[0797]

[0798] Ex.3-67:

[0799]

[0800] Ex.3-68 and 69:

[0801]

[0802] Ex.3-70:

[0803]

[0804] Ex.3-71-72:

[0805]

[0806] Ex.3-73-75:

[0807]

[0808] Ex.3-76-78:

[0809]

[0810] Ex.3-79-81:

[0811]

[0812] Ex.3-82-84:

[0813]

[0814] Ex.3-85-87:

[0815]

[0816] Ex.3-88-90:

[0817]

[0818] Ex.3-91-93:

[0819]

[0820] Ex.3-94-96:

[0821]

[0822] Example 4: Tetradentate platinum and palladium complexes with narrow-band emission using analogs of bicarbazole and phenyl-imidazole carbene thing

[0823] In the present invention, a series of platinum (II) and palladium (II) complexes with narrow-band emission based on bicarbazole and phenyl-imidazole carbene analogs have been designed. Such emitters can be used in full-color display and lighting applications.

[0824] FWHM (full width at half maximum) is an important property for improving color purity. When designing OLED emitters, the second lowest triplet energy state (T 2 ) emission and the broad emission caused by electron vibration coupling are the main obstacles to be overcome. 1 Energy or increase T 2 Energy to increase T 1 and T 2 The energy gap between them can effectively suppress T 2 emission( Fig.17 ). In PtON5S56-m, the extended conjugation on the carbazole ring makes T 1 The energy level is reduced, so that at T 1 and T 2 The larger energy gap between them is generated. Thus, narrow-band emission is achieved at room temperature. The photoluminescence spectra of the exemplary compounds PtON5S56-m and PtON5S56-mtb are shown in Fig.19 The photoluminescence spectra of the exemplary compounds PtON5NS56-m and PtON5S56-dpm are presented in Fig. 20 The photoluminescence spectrum of another exemplary compound is shown in Fig.21 middle.

[0825] The compound can be synthesized by the following method: Ex.1

[0826]

[0827] Ex.2

[0828]

[0829] Ex.3

[0830]

[0831] Ex.4

[0832]

[0833] Ex.5

[0834]

[0835] Ex.6

[0836]

[0837] Ex.7

[0838]

[0839] Ex.8

[0840]

[0841] Ex.9

[0842]

[0843] Ex.10

[0844]

[0845] Ex.11

[0846]

[0847] Ex.12

[0848]

[0849] Ex.13

[0850]

[0851] Ex.14

[0852]

[0853] Ex.4-1:

[0854]

[0855] Ex.4-2:

[0856]

[0857] Ex.4-3:

[0858]

[0859] Ex.4-4:

[0860]

[0861] Ex.4-5:

[0862]

[0863] Ex.4-6:

[0864]

[0865] Ex.4-7:

[0866]

[0867] Ex.4-8:

[0868]

[0869] Ex.4-9:

[0870]

[0871] Ex.4-10:

[0872]

[0873] Ex.4-11:

[0874]

[0875] Ex.4-12:

[0876]

[0877] Ex.4-13:

[0878]

[0879] Ex.4-14:

[0880]

[0881] Ex.4-15:

[0882]

[0883] Ex.4-16:

[0884]

[0885] Ex.4-17:

[0886]

[0887] Ex.4-18:

[0888]

[0889] Ex.4-19:

[0890]

[0891] Ex.4-20:

[0892]

[0893] Ex.4-21:

[0894]

[0895] Ex.4-22:

[0896]

[0897] Ex.4-23:

[0898]

[0899] Ex.4-24:

[0900]

[0901] Ex.4-25:

[0902]

[0903] Ex.4-26:

[0904]

[0905] Ex.4-27:

[0906]

[0907] Ex.4-28:

[0908]

[0909] Ex.4-29:

[0910]

[0911] Ex.4-30:

[0912]

[0913] Ex.4-31:

[0914]

[0915] Ex.4-32:

[0916]

[0917] Ex.4-33:

[0918]

[0919] Ex.4-34:

[0920]

[0921] Ex.4-35:

[0922]

[0923] Ex.4-36:

[0924]

[0925] Ex.4-37:

[0926]

[0927] Ex.4-38:

[0928]

[0929] Ex.4-39:

[0930]

[0931] Ex.4-40:

[0932]

[0933] Ex.4-41:

[0934]

[0935] Ex.4-42:

[0936]

[0937] Ex.4-43:

[0938]

[0939] Ex.4-44:

[0940]

[0941] Ex.4-45:

[0942]

[0943] Ex.4-46:

[0944]

[0945] Ex.4-47:

[0946]

[0947] Ex.4-48:

[0948]

[0949] Ex.4-49:

[0950]

[0951] Ex.4-50:

[0952]

[0953] Ex.4-51:

[0954]

[0955] Ex.4-52:

[0956]

[0957] Example 5: Phenyl-pyridine-based tetradentate platinum complexes with narrow emission spectra in the green and red emission range Object emitter

[0958] Through the design of rigid tetradentate metal complexes, a narrow-band emitter with a small spectral difference between the emission at 77 K and the emission at room temperature was designed. In addition, potential fragments of carbazole and its analogs were incorporated into the emitter to reduce the electronic vibration characteristics of its emission spectrum at 77 K, thereby further minimizing its emission spectrum bandwidth.

[0959] The PL spectrum of Pt3O5-tbm in dichloromethane solution at room temperature is shown in Fig. 22 middle.

[0960] The compound can be synthesized by:

[0961] Ex.1

[0962]

[0963] Ex.2

[0964]

[0965] Ex.3

[0966]

[0967] Ex.4

[0968]

[0969] Ex.5

[0970]

[0971] Ex.6

[0972]

[0973] Ex.7 / 8

[0974]

[0975] Ex.9

[0976]

[0977] The disclosure of each patent, patent application, and publication cited herein is hereby incorporated by reference in its entirety. Although the present invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of the present invention may be devised by other skilled in the art without departing from the true spirit and scope of the present invention. The appended claims are intended to be interpreted as including all such embodiments and equivalent variations.

Claims

1. A compound represented by formula I, in: M represents platinum (Pt) or palladium (Pd); X 1 , X 2 , X 3 and X 4 Coordinated to M and independently N or C; Cy 1 , Cy 2 , Cy 4 and Cy 5 Each of is independently a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbene; Cy 3 , Cy 6 and Cy 7 is independently present or absent; wherein each Cy 3 , Cy 6 and Cy 7 are independently substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclyl, carbene or N-heterocyclic carbenes; Among them, when Cy 3 If it does not exist, then B 1 Selected from the group consisting of: CR 8 R 9 , CR 1 =CR 2 , C≡C、C=O、C=S、SiR 8 R 9 、GeR 8 R 9 、NR 10 、PR 10 、R 10 P=O、AsR 10 、R 10 As=O、 O, S, S=O, SO2, Se, Se=O, SeO2, BR 10 ,BiR 10 , R 3 Bi=O、 or B 1 Does not exist and Cy 1 With Cy 2 Connect via a single button; Among them, when Cy 3 If it exists, then B 1 Selected from the group consisting of: CR 8 、SiR 8 ,GeR 8 ,N,P,P=O,As,As=O,B,R 10 Bi=O or Bi, or B 1 Does not exist and Cy 1 With Cy 2 Connect via a single button; Among them, when Cy 6 If it does not exist, then B 2 Selected from the group consisting of: CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 11 R 12 ,GeR 11 R 12 NR 13 , PR 13 , R 13 P=O、AsR 13 , R 13 As=O, O, S, S=O, SO2, Se, Se=O, SeO2, BR 13 ,BiR 13 , R 13 Bi=O、 or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button; Among them, when Cy 6 If it exists, then B 2 Selected from the group consisting of: CR 11 、SiR 11 ,GeR 11 ,N,P,P=O,As,As=O,B,R 13 Bi=O or Bi, or B 2 Does not exist and Cy 4 With Cy 5 Connect via a single button; Among them, when Cy 7 If it does not exist, then A 4 does not exist and B 2 Yes A 8 ; Among them, when Cy 7 If it exists, then B 2 Selected by CR 14 、SiR 14 ,GeR 14 ,N,P,P=O,As,As=O,B,R 14 Bi=O or Bi; A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of is independently absent or present, and A 1 , A 2 , A 3 , A 4 , A 5 and A 8 Each of the CR 15 R 16 , CR 15 =CR 16 , C≡C, C=O, C=S, SiR 15 R 16 ,GeR 15 R 16 NR 17 , PR 17 , R 17 P=O、AsR 17 , R 17 As=O, O, S, S=O, SO2, Se, Se=O, SeO2, BR 17 ,BiR 17 , R 17 Bi=O、 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silane, polymeric group; or any conjugate or combination thereof; wherein any two adjacent substituents are optionally joined to form a fused ring of Formula A, Formula B, Formula C, or Formula D: A 6 and A 7 Each of which is independently a single bond, CR 1 R 2 , CR 1 =CR 2 , C≡C, C=O, C=S, SiR 1 R 2 ,GeR 1 R 2 NR 3 , PR 3 , R 3 P=O、AsR 3 , R 3 As=O, O, S, S=O, SO2, Se, Se=O, SeO2, BR 3 ,BiR 3 , R 3 Bi=O、 Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Each of is independently N, C, P, O, S or Si; Each R 7 and R 8 is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 7 and R 8 independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof; wherein any two adjacent substituents may further be joined to form a fused ring; and Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 One or more of optionally represents R X , where R X is a bulky substituent selected from the group consisting of branched alkyl, cycloalkyl, bicyclic, fused bicyclic, adamantyl, ferrocenyl, dialkylamino, diarylamino, alkylarylamino, trialkylsilyl, tricycloalkylsilyl, triarylsilyl, triheteroarylsilyl, dialkylarylsilyl, alkyldiarylsilyl, alkylarylamino, and optionally substituted: aryl and heteroaryl.

2. The compound according to claim 1, wherein the compound is represented by Formula II: in: G 1 Yes O, NR 1 , CR 1 or S; Y 1 , Y 2 , Y 5 , Y 6 and Y 7 are independently N, C, P, O, S or Si; and At least one R 1 exists and represents R X .

3. The compound of claim 1, wherein the compound is represented by the structure in Listing 1.

4. The compound of claim 1, wherein the compound is represented by the structure in Listing 2 or Listing 2A.

5. The compound of claim 1, wherein the compound is represented by the structure in Listing 3.

6. The compound according to claim 1, wherein the compound is represented by formula III: in: Y 5 , Y 6 and Y 7 Each of is independently N, C, P, O, S or Si; Cy 1 is selected from the group consisting of N-heterocyclic carbenes, carbenes, imidazoles and benzimidazoles; wherein when Cy 1 When it is N-heterocyclic carbene or carbene, X 1 is C and Y 8 is N; and when Cy 1 When it is imidazole or benzimidazole, X 1 is N and Y 8 It is C. X 1 is N; and Y 5 Optionally with R 1 or R 1 The substituents on the amine are fused to form a ring.

7. The compound of claim 1, wherein the compound is represented by the structure in Listing 4.

8. The compound according to claim 6, wherein part Independently is one of the following structures: in: Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 and Y 10 Each of is independently N, C, P, O, S or Si; R 1 , R 2 , R 3 , R 4 Each of R is independently absent or present as a single substituent or multiple substituents as valence permits, and each R present is 1 , R 2 , R 3 , R 4 independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, arylalkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric group; or any conjugate or combination thereof.

9. The compound of claim 1, wherein the compound is represented by the structure in Listing 5.

10. The compound according to claim 5, wherein Cy 1 represents N-heterocyclic carbene; X 1 represents C; and Two adjacent substituents R 3 are present and taken together represent a group of formula C.

11. The compound of claim 1, wherein the compound is represented by the structure in Listing 6.

12. The compound of claim 1, wherein the compound is represented by the structure in Listing 7 or Listing 7A.

13. The compound according to claim 1, wherein A 1 Does not exist; Cy 1 is a heteroaryl group; X 1 is N; and two adjacent substituents R 1 , two adjacent substituents R 2 , two adjacent substituents R 3 or two adjacent substituents R 7 are present and taken together represent a group of formula C.

14. The compound of claim 1, wherein the compound is represented by the structure in Listing 8.

15. The compound according to claim 1, wherein B 1 does not exist; B 2 does not exist; Cy 1 is a heteroaryl group; X 1 is N; and structure express wherein R' and R" independently represent hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, isocyano, sulfinyl, mercapto, sulfonic acid, carboxyl, hydrazine; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramide, silanyl, polymeric groups, or any conjugate or combination thereof; and Each occurrence of R" represents aryl or heteroaryl; Wherein any two adjacent groups R' or R" are optionally joined to form a fused ring, which is optionally further substituted.

16. The compound according to claim 1, wherein B 1 does not exist; Cy 1 represents a heteroaryl group; X 1 is N; and Two adjacent substituents R 1 , two adjacent substituents R 2 , two adjacent substituents R 3 or two adjacent substituents R 7 The presence and taken together represent a group of formula C.

17. The compound of claim 1, wherein the compound is represented by the structure in Listing 9.

18. The compound of claim 1, wherein the compound is represented by the structure in Listing 10.

19. The compound of claim 1, wherein the compound is represented by the structure in Listing 11 or Listing 11A.

20. An organic electroluminescent device comprising the compound according to claim 1.

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