WO2022223011A1 - 基于1,8-取代咔唑的高辐射速率铂配合物及应用 - Google Patents

基于1,8-取代咔唑的高辐射速率铂配合物及应用 Download PDF

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WO2022223011A1
WO2022223011A1 PCT/CN2022/088329 CN2022088329W WO2022223011A1 WO 2022223011 A1 WO2022223011 A1 WO 2022223011A1 CN 2022088329 W CN2022088329 W CN 2022088329W WO 2022223011 A1 WO2022223011 A1 WO 2022223011A1
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group
substituted
light
emitting
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French (fr)
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李贵杰
佘远斌
郑建兵
许克伟
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浙江工业大学
浙江华显光电科技有限公司
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Priority to MX2023012422A priority Critical patent/MX2023012422A/es
Priority to KR1020237039622A priority patent/KR20230170775A/ko
Priority to JP2023564470A priority patent/JP2024518728A/ja
Publication of WO2022223011A1 publication Critical patent/WO2022223011A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • C—CHEMISTRY; METALLURGY
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Definitions

  • the invention belongs to the field of luminescent materials, and in particular relates to a high radiation rate platinum complex based on 1,8-substituted carbazole and its application.
  • OLED organic electroluminescent device
  • Light-emitting materials are the core materials of OLED devices, but stable and efficient light-emitting materials that can meet commercial applications are still extremely rare, especially phosphorescent and delayed fluorescent materials with high quantum efficiency. Therefore, the design and development of new high-performance light-emitting materials is still an important direction to promote the development of the OLED field. In addition, the stability of OLED devices is still a bottleneck restricting its development, and the radiation rate (k r obs ) of luminescent materials is an important factor affecting the stability of OLED devices.
  • Increasing the radiation rate of the luminescent material molecules can make the molecules emit light efficiently; at the same time, shorten the time that the molecules are in the excited state, reduce the molecular excited state lifetime ⁇ obs , and reduce or avoid the occurrence of triplet-triplet exciton annihilation to produce high-energy singlet
  • the thermal energy generated by the non-radiative relaxation of excited state molecules is reduced, and the stability of material molecules and OLED devices is improved. Therefore, the design and development of luminescent materials with high radiation rate k r obs and short excited state lifetime ⁇ obs is of great significance for improving the stability of material molecules and OLED devices.
  • the purpose of the present invention is to provide a high radiation rate platinum complex based on 1,8-substituted carbazole and its application in view of the deficiencies of the prior art.
  • the luminescent material of the present invention is based on a tetradentate ring metal platinum(II) complex containing 1,8-substituted carbazole and a phenylcarbazole molecular core, and has a high radiation rate k r obs and a short excited state lifetime ⁇ obs .
  • L is a five- or six-membered heteroaromatic ring.
  • R a nor R b is a hydrogen atom and each independently represents an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heteroaryl, halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, ureido, alkynyloxy, ester, amido, sulfonyl, sulfinyl , sulfonylamine, phosphorylamine, alkoxycarbonylamine, aryloxycarbonylamine, silyl, alkylamine, dialkylamine, monoarylamine, bisarylamine group, ureido group, imino group, or a combination thereof.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl , substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, ureido, alkynyloxy, ester , amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, A monoarylamine group, a bisarylamine group, a ureidoidene group, an imine group, or
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be connected to form a condensed ring, and the condensed ring may also be condensed with other rings.
  • R u , R v , R w , R x and R y each independently represent mono-, di-, tri-, tetra- or unsubstituted, and R u , R v , R w , R x and R y each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, Halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, urea, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamine, phosphorylamine alkoxycarbonylamine, aryloxycarbonylamine, silyl, alkylamine, bis
  • R is not an alkyl group other than methyl, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted group of heteroaryl, or its deuterated substituent.
  • the organic light-emitting element is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.
  • a light-emitting device comprising a first electrode, a second electrode and an organic layer; the organic layer is arranged between the first electrode and the second electrode, and has at least one organic layer; the organic layer includes the above-mentioned light-emitting material.
  • the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer or an active layer, an electron blocking layer or an electron transport layer.
  • a display device includes the above-mentioned light-emitting device.
  • the dihedral angle between the substituted carbazole ring and the pyridine ring can be increased, the conjugation between the two can be reduced, and the molecular excitation of the material can be regulated.
  • the increase of metal-to-ligand charge transfer state (MLCT) greatly increases the composition, improves the intersystem crossing rate of the molecule, thereby increases the radiation rate k r obs and shortens the excited state lifetime ⁇ obs ; at the same time, it improves the phosphorescence quantum efficiency of the material molecule. ;
  • the increase of the dihedral angle between the substituted carbazole ring and the pyridine ring can improve the rigidity of the molecule, effectively reduce the energy consumed by the vibration and rotation of the carbazole ring in the molecule, reduce the non-radiative attenuation, and improve the phosphorescence quantum efficiency.
  • Figure 1 is a schematic diagram of the optimized molecular structures of PtPN1-Cz and PtDMCz calculated by density functional theory (DFT) and the corresponding dihedral angles between carbazole/pyridine and 1,8-dimethyl/pyridine;
  • DFT density functional theory
  • FIG. 2 is a schematic diagram of the comparison of the emission spectra of PtON1-Cz in various environments; wherein, 2-MeTHF is 2-methyltetrahydrofuran, DCM is dichloromethane, and RT represents room temperature;
  • Fig. 3 is a schematic diagram comparing the emission spectra of PtDMCz in various environments; wherein, 2-MeTHF is 2-methyltetrahydrofuran, DCM is dichloromethane, PMMA is polymethyl methacrylate, and RT represents room temperature;
  • Figure 4 is a schematic diagram of the luminescence intensity decay curve of PtDMCz in dichloromethane solution at room temperature; wherein, DCM is dichloromethane, and RT represents room temperature;
  • Figure 5 shows the emission spectra of PtDMCz, PtDMCz-ppz, PtDMCz-2-ptz, PtDMCz-1-ptz, PtDMCz-piz, PtDMCz-ppy, PtDMCz-NHC and PtDMCz-Ph-NHC in dichloromethane solution at room temperature ;
  • Figure 6 is a comparison of the photostability test of PtDMCz and PdDMCz
  • FIG. 7 is a schematic structural diagram of an organic light-emitting element; wherein the substrate, the anode, the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer and the cathode are shown in order from bottom to top.
  • a high radiation rate platinum complex luminescent material based on 1,8-substituted carbazole of the present invention is a tetradentate ring metal platinum (II) complex containing 1,8-bis-substituted carbazole, and the chemical formula is as shown in the general formula (1 ) as shown:
  • L is a five- or six-membered heteroaromatic ring.
  • R a nor R b is a hydrogen atom and each independently represents an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heteroaryl, halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, ureido, alkynyloxy, ester, amido, sulfonyl, sulfinyl , sulfonylamine, phosphorylamine, alkoxycarbonylamine, aryloxycarbonylamine, silyl, alkylamine, dialkylamine, monoarylamine, bisarylamine group, ureido group, imino group, or a combination thereof.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl , substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, ureido, alkynyloxy, ester , amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, Monoarylamine group, biarylamine group, ureido group, imino group or combination thereof, two or more of R
  • R u , R v , R w , R x and R y each independently represent mono-, di-, tri-, tetra- or unsubstituted, and R u , R v , R w , R x and R y each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, Halogen, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazine, urea, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamine, phosphorylamine alkoxycarbonylamine, aryloxycarbonylamine, silyl, alkylamine, bis
  • the present invention can specifically be one of the following chemical structures, but is not limited to this:
  • R is not an alkyl group other than methyl, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted group of heteroaryl, or its deuterated substituent.
  • the above-mentioned 1,8-substituted carbazole-based platinum complex light-emitting material of the present invention can be used as a phosphorescent light-emitting material or a delayed fluorescent material in an organic light-emitting element.
  • the organic light-emitting element is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.
  • the present invention also provides a light-emitting device, comprising a first electrode, a second electrode and an organic layer; the light-emitting material of the present invention is used as the organic layer therein, is arranged between the first electrode and the second electrode, and at least one organic layer.
  • the terms "optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • compositions described herein are disclosed, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these materials are disclosed, although specific references to each different individual and collective combination and permutation of these compounds are not specifically disclosed. , but each has its own specific assumptions and descriptions. For example, if a specific compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then every combination and permutation of the compound and possible modifications are specifically contemplated unless specifically stated to the contrary possible modifications.
  • Linking atoms used in the present invention are capable of linking two groups, eg, linking N and C.
  • the linking atom can optionally (if the valence allows) attach other chemical groups.
  • an oxygen atom would not have any other chemical group attached, as a valence bond is already satisfied once two atoms (eg, N or C) are bonded.
  • carbon is the linking atom
  • two additional chemical groups can be attached to the carbon atom.
  • cyclic structure refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclyl Ring Carbine.
  • substituted or similar terms as used herein includes all permissible substituents of organic compounds.
  • the permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds.
  • exemplary substituents include those described below.
  • the permissible substituents may be one or more, the same or different.
  • a heteroatom eg, nitrogen
  • the present invention is not intended to be limited in any way by the permissible substituents of organic compounds.
  • substituted or “substituted with” include the implied condition that the substitution complies with the substituted atom and the permissible valency of the substituent, and that the substitution results in a stable compound (e.g., that does not spontaneously undergo transformation ( Compounds such as by rearrangement, cyclization, elimination, etc.).
  • individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted) unless explicitly stated to the contrary.
  • R 1 ", “R 2 ", “R 3 " and “R 4 " are used in the present invention as general symbols to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in the present invention, when they are defined as some substituents in one instance, they may also be defined as some other substituents in another instance.
  • alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 30 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 alkyl, eicosyl, tetracosyl, etc.
  • the alkyl group can be cyclic or acyclic.
  • the alkyl group can be branched or unbranched.
  • the alkyl group can also be substituted or unsubstituted.
  • the alkyl group can replace one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, methyl, etc. described herein.
  • a "lower alkyl” group is an alkyl group containing from 1 to 6 (eg, 1 to 4) carbon atoms.
  • alkyl generally refers to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the particular substituent on the alkyl group.
  • halogenated alkyl or “haloalkyl” specifically refers to an alkyl group substituted with one or more halogens (eg, fluorine, chlorine, bromine, or iodine).
  • alkoxyalkyl specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below.
  • alkylamino specifically refers to an alkyl group substituted with one or more amino groups, as described below and the like.
  • alkyl is used in one instance and a specific term such as “alkyl alcohol” is used in another, it is not meant to imply that the term “alkyl” does not simultaneously refer to a specific term such as “alkyl alcohol” Alcohol” etc.
  • cycloalkyl as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms composed of at least three carbon atoms.
  • examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like.
  • heterocycloalkyl is a class of cycloalkyl groups as defined above and is included within the meaning of the term “cycloalkyl” wherein at least one ring carbon atom is replaced by a heteroatom such as but not limited to nitrogen, oxygen, sulfur or phosphorus replace.
  • the cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted.
  • the cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro as described in the present invention , silyl groups, sulfur-oxo groups and mercapto groups.
  • alkoxy and “alkoxy group” as used herein refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether linkage; that is, “alkoxy” can be defined as— OR 1 , wherein R 1 is alkyl or cycloalkyl as defined above.
  • Alkoxy also includes the alkoxy polymers just described; that is, the alkoxy group can be a polyether, such as -OR 1 -OR 2 or -OR 1 -(OR 2 ) a -OR 3 , where "a” is an integer from 1 to 500, and R 1 , R 2 and R 3 are each independently alkyl, cycloalkyl, or a combination thereof.
  • alkenyl as used herein is a hydrocarbon group of 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon double bond.
  • the alkenyl can be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or mercapto.
  • groups including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or mercapto.
  • Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like.
  • heterocycloalkenyl is a class of cycloalkenyl groups as defined above and is included within the meaning of the term “cycloalkenyl” wherein at least one carbon atom of the ring is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus substitution. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted.
  • the cycloalkenyl and heterocycloalkenyl may be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkenyl, and cycloalkenyl groups described in the present invention.
  • alkynyl as used in the present invention is a hydrocarbon group having 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon triple bond.
  • Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups, cycloalkenyl groups, alkynyl groups described herein. , cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo or mercapto.
  • cycloalkynyl as used herein is a non-aromatic carbon-based ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond.
  • cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like.
  • heterocycloalkynyl is a cycloalkenyl group as defined above and is included within the meaning of the term “cycloalkynyl” wherein at least one of the carbon atoms of the ring is replaced by a heteroatom, the heteroatom Atoms such as but not limited to nitrogen, oxygen, sulfur or phosphorus.
  • Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkyne described in the present invention group, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo group, or mercapto.
  • groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkyne described in the present invention group, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester
  • aryl refers to any carbon-based aromatic group of 60 carbon atoms or less, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like.
  • aryl also includes "heteroaryl,” which is defined as an aromatic-containing group containing at least one heteroatom in the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • non-heteroaryl (which is also included in the term “aryl”) defines an aromatic-containing group that does not contain heteroatoms.
  • Aryl groups can be substituted or unsubstituted.
  • Aryl can 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, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo or mercapto.
  • the term "biaryl” is a specific type of aryl group and is included in the definition of "aryl”. Biaryl refers to two aryl groups joined together through a fused ring structure, as in naphthalene, or two aryl groups joined through one or more carbon-carbon bonds, as in biphenyl.
  • amine or “amino” as used herein is represented by the formula —NR1R2 , wherein R1 and R2 can be independently selected from hydrogen , alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, selected from cycloalkynyl, aryl or heteroaryl.
  • alkylamino as used herein is represented by the formula -NH(-alkyl), wherein the alkyl group is as described herein.
  • Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, isopentyl Amino, tert-amylamino, hexylamino, etc.
  • dialkylamino as used in the present invention is represented by the formula -N(-alkyl) 2 , wherein the alkyl group is as described in the present invention.
  • Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino , Diamylamino, Diisoamylamino, Di-tert-amylamino, Dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N -propylamino etc.
  • carboxylic acid as used in the present invention is represented by the formula -C(O)OH.
  • esters used in the present invention is represented by the formula -OC(O)R 1 or -C(O)OR 1 , wherein R 1 can be the alkyl, cycloalkyl, alkenyl, cycloalkenyl described in the present invention , alkynyl, cycloalkynyl, aryl or heteroaryl.
  • polyester as used in the present invention is represented by the formula -(R 1 O(O)CR 2 -C(O)O) a - or -(R 1 O(O)CR 2 -OC(O)) a - , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and "a” is 1 to An integer of 500.
  • the term “polyester” is used to describe groups produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.
  • ether as used in the present invention is represented by the formula R 1 OR 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described in the present invention aryl, aryl or heteroaryl.
  • polyether used in the present invention is represented by the formula —(R 1 OR 2 O) a —, wherein R 1 and R 2 can be independently alkyl, cycloalkyl, alkenyl, cycloalkene as described in the present invention alkynyl, alkynyl, cycloalkynyl, aryl or heteroaryl and "a" is an integer from 1 to 500.
  • Examples of polyether groups include polyethylene oxide, polypropylene oxide and polybutylene oxide.
  • halogen refers to the halogens fluorine, chlorine, bromine and iodine.
  • heterocyclyl refers to monocyclic and polycyclic non-aromatic ring systems
  • heteroaryl refers to monocyclic and polycyclic no more than 60 carbon atoms
  • An aromatic ring system wherein at least one of the ring members is not carbon.
  • the term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and oxazolyl of 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, Pyrimidyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, including 1,2,3,4-tetrazolyl and 1 , tetrazolyl of 2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadia
  • hydroxyl as used in the present invention is represented by the formula -OH.
  • ketone used in the present invention is represented by the formula R 1 C(O)R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne as described in the present invention alkynyl, cycloalkynyl, aryl or heteroaryl.
  • nitro used in the present invention is represented by the formula -NO 2 .
  • nitrile as used in the present invention is represented by the formula -CN.
  • sil used in the present invention is represented by the formula —SiR 1 R 2 R 3 , wherein R 1 , R 2 and R 3 can be independently hydrogen or alkyl, cycloalkyl, alkoxy as described in the present invention alkenyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
  • mercapto used in the present invention is represented by the formula -SH.
  • R1", R2", R3 ", " Rn " (where n is an integer ) as used herein may independently have one or more of the above-listed groups.
  • R1 is a straight chain alkyl group
  • one hydrogen atom of the alkyl group may be optionally substituted with a hydroxy, alkoxy, alkyl, halo, and the like.
  • the first group may be incorporated within the second group, or the first group may be pendant (ie, attached) to the second group.
  • the amino group may be incorporated within the backbone of the alkyl group.
  • the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.
  • the compounds of the present invention may contain "optionally substituted” moieties.
  • substituted means that one or more hydrogens of the specified moiety are replaced with a suitable substituent.
  • 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 selected from one of the specified groups When the above substituents are substituted, the substituents may be the same or different at each position.
  • Combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. It is also contemplated that, in certain aspects, unless expressly stated to the contrary, each substituent may be further optionally substituted (ie, further substituted or unsubstituted).
  • R n is usually an integer. That is, R n is understood to represent the five individual substituents R n(a) , R n(b) , R n(c) , R n(d) , R n(e) . "Individual substituents" means that each R substituent may be independently defined. For example, if in one instance Rn(a) is halogen, then Rn(b) in that instance is not necessarily halogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. are mentioned several times in the chemical structures and units disclosed and described herein. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. in the specification applies to any structure or units, unless otherwise stated.
  • fused ring used in the present invention means that two adjacent substituents can be fused into a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc., and saturated six- or seven-membered carbocyclic or carboheterocycles, etc.
  • a heteroaromatic ring such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc.
  • organic optoelectronic devices using organic materials are becoming increasingly urgent for several reasons. Many of the materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages of inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, can make them well suited for special applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which organic light-emitting layers emit light can often be easily tuned with appropriate dopants.
  • blue electroluminescent devices are still the most challenging field in this technology so far, and the stability of blue devices is a major issue.
  • the choice of host material has been shown to be very important for the stability of blue devices.
  • the triplet excited state (T 1 ) minimum energy of the blue light-emitting material is very high, which means that the triplet excited state (T 1 ) minimum energy of the host material of the blue device should be higher. This makes the development of host materials for blue devices more difficult.
  • the metal complexes of the present invention can be tailored or tuned to specific applications where specific emission or absorption properties are desired.
  • the optical properties of the metal complexes in the present disclosure can be tuned by changing the structure of the ligand surrounding the metal center or by changing the structure of the fluorescent emitter on the ligand.
  • metal complexes of ligands with electron-donating substituents or electron-withdrawing substituents can often exhibit different optical properties in emission and absorption spectra.
  • the color of the metal complexes can be tuned by modifying the fluorescent emitters and the conjugated groups on the ligands.
  • the emission of such complexes of the invention can be tuned, for example, by changing the ligand or fluorescent emitter structure, eg from ultraviolet to near infrared.
  • a fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, and the singlet excitons rapidly decay to produce instant light emission.
  • the complexes of the present invention can provide emission in most of the visible spectrum.
  • the complexes of the present invention can emit light in the range of about 400 nm to about 700 nm.
  • the complexes of the present invention have improved stability and efficiency relative to conventional emission complexes.
  • the complexes of the present invention can be used as luminescent labels, for example, in biological applications, anticancer agents, emitters in organic light emitting diodes (OLEDs), or combinations thereof.
  • the complexes of the present invention can be used in light emitting devices such as compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.
  • platinum-containing compounds or complex complexes Disclosed herein are platinum-containing compounds or complex complexes.
  • compound or complex are used interchangeably herein. Additionally, the compounds disclosed herein have a neutral charge.
  • the compounds disclosed herein can exhibit desirable properties and possess emission and/or absorption spectra that can be tuned by selection of appropriate ligands.
  • the invention may exclude any one or more of the compounds, structures or portions thereof specifically recited herein.
  • the compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices including, but not limited to, light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of light absorption and emission compatible and Used as a marker for biological applications.
  • light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of light absorption and emission compatible and Used as a marker for biological applications.
  • OLEDs organic light emitting diodes
  • the disclosed compounds are platinum complexes.
  • the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.
  • the compounds disclosed herein can be used in a variety of applications.
  • the compound can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.
  • OLEDs organic light-emitting diodes
  • the compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the Examples provided herein.
  • the compounds disclosed herein can be delayed fluorescent and/or phosphorescent emitters. In one aspect, the compounds disclosed herein can be delayed fluorescent emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. On the other hand, the compounds disclosed herein can be delayed fluorescent emitters and phosphorescent emitters.
  • the present disclosure relates to cyclometallic platinum complexes that can be used as light-emitting and host materials in OLED devices.
  • High-resolution mass spectra were measured on an ESI-QTOF mass spectrometer of Applied Biosystems, and the sample ionization mode was electrospray ionization.
  • Example 1 Four-dentate ring metal platinum (II) complex phosphorescent light-emitting material PtDMCz synthetic route is as follows:
  • ligand 1 Compound 4 (1.00 g, 2.83 mmol, 1.0 equiv), compound 5 (955 mg, 3.11 mmol, 1.1 equiv), three (two benzylideneacetone) dipalladium (104mg, 0.11mmol, 4mol%), ligand JohnPhos (68mg, 0.23mmol, 8mol%), sodium tert-butoxide (544mg, 5.66mmol, 2.0 equiv), then purge nitrogen three times, Toluene (30 mL) and dioxane (30 mL) were added under nitrogen.
  • Tetradentate ring metal platinum (II) complex phosphorescent material PtDMCz-2-ptz synthetic route is as follows:
  • the mixture was stirred and reacted in an oil bath at 100°C for 2 days, monitored by thin layer chromatography until the reaction of the starting materials was completed, and cooled to room temperature.
  • Ethyl acetate was added, washed twice with water, the aqueous layer was extracted twice with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography. rate 87%.
  • Tetradentate ring metal platinum (II) complex phosphorescent material PtDMCz-1-ptz synthetic route is as follows:
  • the mixture was stirred and reacted in an oil bath at 100°C for 2 days, monitored by thin layer chromatography until the reaction of the starting materials was completed, and cooled to room temperature.
  • Ethyl acetate was added, washed twice with water, the aqueous layer was extracted twice with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography. rate 85%.
  • Example 4 Four-dentate ring metal platinum (II) complex phosphorescent material PtDMCz-piz synthesis route is as follows:
  • Example 5 The synthetic route of the tetradentate ring metal platinum (II) complex phosphorescent material PtDMCz-ppy is as follows:
  • Tetradentate ring metal platinum (II) complex phosphorescent material PtDMCz-NHC synthetic route is as follows:
  • the obtained gray solid was added to methanol/water (40mL/4mL), stirred and dissolved, and added with Ammonium fluorophosphate (302 mg, 1.85 mmol, 1.5 equiv) was stirred at room temperature for 3 days. Water was added, most of the methanol was evaporated under reduced pressure, filtered, washed with water and then with petroleum ether, and dried to obtain the ligand DMCz-NHC, gray solid 810 mg, yield 81%.
  • Example 7 Tetradentate ring metal platinum (II) complex phosphorescent light-emitting material PtDMCz-Ph-NHC synthetic route is as follows:
  • the obtained gray solid was added to methanol/water (40mL/4mL), stirred and dissolved, and added with Ammonium fluorophosphate (140 mg, 0.86 mmol, 1.5 equiv) was stirred at room temperature for 3 days. Water was added, most of the methanol was evaporated under reduced pressure, filtered, washed with water and then with petroleum ether, and dried to obtain the ligand DMCz-Ph-NHC as a gray solid, 364 mg, with a yield of 74%.
  • Example 8 Four-dentate ring metal platinum (II) complex phosphorescent light-emitting material PtDMCz-ppz synthetic route is as follows:
  • Table 1 Data list of photophysical properties of tetradentate ring metal platinum(II) complex luminescent materials
  • the dihedral angle is the angle between the pyridine ring and its 4-position carbazole ring.
  • the dihedral angles between (substituted) carbazole/pyridine in PtON1-Cz and PtDMCz after optimization of the structure by theoretical calculation are 51 o and 88 o , respectively, indicating that the 1,8
  • the introduction of a methyl group at the - position can greatly increase the dihedral angle between substituted carbazoles/pyridines.
  • the increase of the dihedral angle can improve the rigidity of the molecule, effectively reduce the energy consumed by the vibration and rotation of the carbazole ring in the molecule, reduce the non-radiative attenuation, and improve the radiative transition rate of the material molecule.
  • PtON1-Cz is a spectrum with a fine vibrational structure, which is a typical charge transfer state (CT) luminescence; while PtDMCz is smooth and lacking.
  • CT charge transfer state
  • MLCT metal-to-ligand charge transfer state
  • the excited state lifetime in methane solution is shortened to 1.1 microseconds ( ⁇ s); at the same time, due to the increase of the dihedral angle between the substituted carbazole ring and the pyridine ring, the molecular rigidity can be improved, effectively reducing the vibration and rotation of the carbazole ring in the molecule.
  • the energy consumed reduces non-radiative decay and increases the phosphorescence quantum efficiency to 88%.
  • PtDMCz has a significantly improved stability than its corresponding palladium(II) complex, PdDMCz.
  • organic light-emitting element carriers are injected into the light-emitting material from the positive and negative electrodes, and the light-emitting material in the excited state is generated and made to emit light.
  • the complex of the present invention represented by the general formula (1) can be applied to an excellent organic light-emitting element such as an organic photoluminescent element or an organic electroluminescent element as a phosphorescent light-emitting material.
  • the organic photoluminescence element has a structure in which at least a light-emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed.
  • the organic layer includes at least a light-emitting layer, and may be composed of only the light-emitting layer, or may have one or more organic layers in addition to the light-emitting layer.
  • organic layers include hole transport layers, hole injection layers, electron blocking layers, hole blocking layers, electron injection layers, electron transport layers, exciton blocking layers, and the like.
  • the hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may also be an electron injection transport layer having an electron injection function.
  • FIG. 7 A schematic diagram of the structure of a specific organic light-emitting element is shown in FIG. 7 . In Fig.
  • the phosphorescent light-emitting material of the present invention is doped into a host material as a guest material to make a light-emitting layer, which can be applied to an OLED device, and the structure is expressed as:
  • ITO/HATCN(10nm)/TAPC(65nm)/mCBP compounds represented in the examples (4-20wt.%,20nm)/PPT(2nm)/Li2CO3: Bepp2 ( 5 %,30nm)/ Li 2 CO 3 (1nm)/Al(100nm)
  • ITO is the transparent anode
  • HATCN is the hole injection layer
  • TAPC is the hole transport layer
  • mCBP is the host material
  • the represented compound (4-20wt.% is the doping concentration, 20nm is the thickness of the light-emitting layer) is the guest Materials
  • PPT is the hole blocking layer
  • Li 2 CO 3 : Bepp 2 is the electron transport layer
  • Li 2 CO 3 is the electron injection layer
  • Al is the cathode. Numbers in nanometers (nm) in parentheses are the thickness of the films.
  • the external quantum efficiency (EQE) of the OLED device using PtDMCz as the doped light-emitting material can reach more than 20%, and it has a small efficiency roll-off, which is obviously better than the comparison in the same device structure.
  • Device performance of doped luminescent material PtON1-Cz It is believed that through the optimization of the device structure and the improvement of the host material, the device performance will be further improved.
  • the structure is an example of an application of the light-emitting material of the present invention, and does not constitute a limitation of the specific OLED device structure of the light-emitting material shown in the present invention, and the phosphorescent light-emitting material is not limited to the compounds shown in the examples.
  • the molecular formula of the applied material in the device is as follows:
  • Each layer of the organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion plating, etc., or wet film formation such as spin coating, printing, printing, etc.
  • the solvent used is not particularly limited.
  • the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, particularly preferably selected from the following structures, but does not represent the present invention
  • the hole transport material can be preferably selected from known or unknown materials, particularly preferably selected from the following structures, but does not represent the present invention
  • the invention is limited to the following structures:
  • the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants.
  • the preferred p-type dopant of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:
  • the electron transport layer can be selected from at least one of compounds ET-1 to ET-13, but it does not mean that the present invention is limited to the following structures:
  • the electron transport layer may be formed of an organic material together with one or more n-type dopants such as LiQ.
  • the compound shown in Example 1 was used as a circularly polarized light-emitting material in an OLED device, and the structure was expressed as: on the glass containing ITO, the hole injection layer (HIL) was HT-1:P-3 (95:5v /v%) with a thickness of 10 nm; the hole transport layer (HTL) is HT-1 with a thickness of 90 nm; the electron blocking layer (EBL) is HT-10 with a thickness of 10 nm, and the emissive layer (EML) is the host Material (H-1 or H-2 or H-3 or H-4 or H-5 or H-6): platinum metal complex of the present invention (95:5 v/v%), thickness 35 nm, electron transport layer (ETL) is ET-13:LiQ (50:50 v/v%) with a thickness of 35 nm, and then the cathode Al was evaporated to 70 nm.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EML

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Abstract

本发明提供了一种基于1,8-取代咔唑的高辐射速率铂配合物及应用。本发明的发光材料通过在咔唑的1,8-位引入取代基，可高效调控材料分子激发态性质，增加金属到配体电荷转移态(MLCT)成分，提高分子的系间窜越速率；同时咔唑的1,8-位引入取代基可增加其和吡啶环之间的二面角增加，可提高分子刚性，有效减少由于分子中咔唑环振动和转动所消耗的能量，减少非辐射衰减。上述因素可共同提高材料分子的辐射速率，缩短激发态寿命。

Description

基于1,8-取代咔唑的高辐射速率铂配合物及应用 技术领域
本发明属于发光材料领域，尤其涉及一种基于1,8-取代咔唑的高辐射速率铂配合物及应用。
背景技术
自美国柯达公司的邓青云博士(C.W.Tang)和VanSlyke于1987年成功制备出第一个高效有机电致发光器件(OLED)以来，历经三十多年的研究，OLED已经发展成为新一代的全彩显示和固态照明技术。OLED是自发光体系，具有制作成本和能耗低、发光效率高、视角广、响应快、等优点，在全彩显示和照明领域具有广阔的应用前景。
发光材料是OLED器件的核心材料，但是稳定高效能够满足商业化应用的发光材料依然及其稀少，尤其是量子效率高的磷光和延迟荧光材料。因此，新型高性能发光材料的设计发展依然是促进OLED领域发展的重要方向。此外，OLED器件的稳定性依然是制约其发展的瓶颈问题，而发光材料的辐射速率(k r obs)是影响OLED器件的稳定性的重要因素。提高发光材料分子的辐射速率可以使分子高效辐射发光；同时缩短分子处于激发态的时间，减小分子激发态寿命τ obs，减少或避免发生三线态-三线态激子湮灭而产生高能量的单线态激子；此外，减少激发态分子非辐射弛豫产生的热能，提高材料分子和OLED器件的稳定性。因此，设计发展具有高辐射速率k r obs和短激发态寿命τ obs的发光材料对于提高材料分子和OLED器件的稳定性具有重要意义。
发明内容
本发明的目的在于针对现有技术的不足，提供一种基于1,8-取代咔唑的高辐射速率铂配合物及应用。本发明发光材料基于苯基咔唑分子母核且含有1,8-取代咔唑的四齿环金属铂(II)配合物，具有高辐射速率k r obs和短激发态寿命τ obs。
本发明的目的是通过以下技术方案来实现的：一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料，是含有1,8-双取代咔唑的四齿环金属铂(II)配合物，化学式如通式(1)所示：
Figure PCTCN2022088329-appb-000001
其中，L为五元或六元杂芳环。
R a和R b均不为氢原子且各自独立地代表烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺 基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R 1、R 2、R 3、R 4、R 5和R 6各自独立地代表氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R 1、R 2、R 3、R 4、R 5和R 6中的两个或者多个可以相连形成稠环，所述稠环还可以与其它环稠合。
R u、R v、R w、R x和R y各自独立地表示单取代、双取代、三取代、四取代或者无取代，且R u、R v、R w、R x和R y各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合；且两个或者多个邻近的R u、R v、R w、R x和R y各自独立或者选择性连接形成稠环。
进一步地，具有如下化学结构中的一种：
Figure PCTCN2022088329-appb-000002
Figure PCTCN2022088329-appb-000003
Figure PCTCN2022088329-appb-000004
其中，R均不为除甲基以外的烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基，或其氘代取代基。
一种上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料在有机发光元件中的应用。
进一步地，所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池。
一种上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料的应用，作为有机发光器件中的磷光发光材料或延迟荧光材料。
一种发光器件，包括第一电极、第二电极和有机层；有机层设置于第一电极和第二电极之间，且至少 有一个有机层；所述有机层包括上述发光材料。
进一步地，所述有机层为空穴注入层、空穴传输层、发光层或活性层、电子阻挡层或电子传输层中至少一层。
一种显示装置，其包括上述发光器件。
本发明的有益效果是：
(1)通过在配体中咔唑的1,8-位引入取代基，可增加取代咔唑环和吡啶环之间的二面角，减小二者之间的共轭，调控材料分子激发态性质，增加金属到配体电荷转移态(MLCT)大大增加成分，提高分子的系间窜越速率，进而提高辐射速率k r obs和缩短激发态寿命τ obs；同时提高材料分子的磷光量子效率；
(2)取代咔唑环和吡啶环之间的二面角增加，可提高分子刚性，有效减少由于分子中咔唑环振动和转动所消耗的能量，减少非辐射衰减，提高磷光量子效率。
附图说明
图1为通过密度泛函理论(DFT)计算得到的PtPN1-Cz和PtDMCz的优化分子结构和对应的咔唑/吡啶和1,8-二甲基/吡啶之间的二面角示意图；
图2为PtON1-Cz在各种环境下的发射光谱图比较示意图；其中，2-MeTHF为2-甲基四氢呋喃，DCM为二氯甲烷，RT代表室温；
图3为PtDMCz在各种环境下的发射光谱图比较示意图；其中，2-MeTHF为2-甲基四氢呋喃，DCM为二氯甲烷，PMMA为聚甲基丙烯酸甲酯，RT代表室温；
图4为PtDMCz在室温下二氯甲烷溶液中的发光强度衰减曲线示意图；其中，DCM为二氯甲烷，RT代表室温；
图5为PtDMCz、PtDMCz-ppz、PtDMCz-2-ptz、PtDMCz-1-ptz、PtDMCz-piz、PtDMCz-ppy、PtDMCz-NHC和PtDMCz-Ph-NHC在室温下二氯甲烷溶液中的发射光谱图；
图6为PtDMCz和PdDMCz的光稳定性测试比较；
图7为有机发光元件的结构示意图；其中，从下到上依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极。
具体实施方式
以下对本发明的内容进行详细说明。以下所记载的构成要件的说明有时是基于本发明的代表性实施方式或具体例而成，但本发明并不限定于此种实施方式或具体例。
本发明一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料，是含有1,8-双取代咔唑的四齿环金属铂(II)配合物，化学式如通式(1)所示：
Figure PCTCN2022088329-appb-000005
其中，L为五元或六元杂芳环。
R a和R b均不为氢原子且各自独立地代表烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R 1、R 2、R 3、R 4、R 5和R 6各自独立地代表氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合，R 1、R 2、R 3、R 4、R 5和R 6中的两个或者多个可以相连形成稠环，所述稠环还可以与其它环稠合。
R u、R v、R w、R x和R y各自独立地表示单取代、双取代、三取代、四取代或者无取代，且R u、R v、R w、R x和R y各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合；且两个或者多个邻近的R u、R v、R w、R x和R y各自独立或者选择性连接形成稠环。
本发明具体可为如下化学结构中的一种，但是不限于此：
Figure PCTCN2022088329-appb-000006
Figure PCTCN2022088329-appb-000007
Figure PCTCN2022088329-appb-000008
Figure PCTCN2022088329-appb-000009
Figure PCTCN2022088329-appb-000010
Figure PCTCN2022088329-appb-000011
Figure PCTCN2022088329-appb-000012
Figure PCTCN2022088329-appb-000013
Figure PCTCN2022088329-appb-000014
Figure PCTCN2022088329-appb-000015
Figure PCTCN2022088329-appb-000016
Figure PCTCN2022088329-appb-000017
Figure PCTCN2022088329-appb-000018
Figure PCTCN2022088329-appb-000019
Figure PCTCN2022088329-appb-000020
Figure PCTCN2022088329-appb-000021
Figure PCTCN2022088329-appb-000022
Figure PCTCN2022088329-appb-000023
Figure PCTCN2022088329-appb-000024
Figure PCTCN2022088329-appb-000025
Figure PCTCN2022088329-appb-000026
Figure PCTCN2022088329-appb-000027
其中，R均不为除甲基以外的烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基，或其氘代取代基。
本发明上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料可作为有机发光元件中的中的磷光发光材料或延迟荧光材料。所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池。
本发明还提供一种发光器件，包括第一电极、第二电极和有机层；本发明的发光材料用作其中的有机层，设置于第一电极和第二电极之间，且至少设有一个有机层。
下面举例说明下述通式(1)代表的本发明的磷光发光材料的具体实例，然而，不解释为限制本发明。
以下对本发明的内容进行详细说明。以下所记载的构成要件的说明有时是基于本发明的代表性实施方式或具体例而成，但本发明并不限定于此种实施方式或具体例。
通过参考以下具体实施方式和其中包含的实施例，可以更容易地理解本公开。在公开和描述本发明的化合物、器件和/或方法之前，应当明白，除非另有说明，否则他们不限于具体的合成方法或者具体的试剂，因为这是可以变化的。也应当明白本发明中使用的术语仅是用于描述特定方面，并不旨在限制。尽管本发明描述的那些类似或者等价的任何方法和材料都可用于该实践或者试验，但现在描述了示例方法和材料。
在说明书和所附权利要求中所用的术语单数形式“一种”、“一个”和“所述”包含复数指代，否则上下文中会另有明确指出。因此，例如提及“组分”时包含两种或多种组分的混合物。
本发明所使用的术语“任选的”或“任选地”意味着随后描述的事件或情况可以或不发生，并且该描述包括所述事件或情况发生的实例及它未发生的实例。
公开了可用于制备本发明所述的组合物的组分，以及要用于本发明中公开的方法中的组合物本身。本发明公开了这些和其它材料，并且应当理解公开了这些物质的组合、子集、相互作用、组等，虽然不能具体地公开这些化合物的每个不同的单独和总的组合以及排列的具体参考，但各自有专门的设想和描述。例如，如果公开和讨论了具体的化合物，并且讨论了能够对许多包含该化合物的分子进行的许多修饰，那么具体地考虑了该化合物的每种组合和排列以及可能进行的修饰，除非特别指出相反的可能修饰。因此，如果公开了一类分子A、B和C以及一类分子D、E和F，和组合分子A-D的实例，那么即使没有单独地记载每一个，但也考虑公开了每个单独地和总的含义组合，A-E、A-F、B-D、B-E、B-F、C-D、C-E和C-F。同样地，也公开了任何子集或这些的组合。例如，A-E、B-F和C-E的子组也是公开的。这一概念适用于本发明的所有方面，包括但不限于制备和使用该组合物的方法中的步骤。因此，如果存在各种另外的步骤能够进行，应当理解，这些另外的步骤各自能够以该方法的具体实施方式或者实施方式的组合进行。
本发明使用的连接原子能够连接两个基团，例如，连接N和C。该连接原子能够任选地(如果价键允许)附接其他的化学基团。例如，氧原子不会具有任何其它的化学基团附接，因为一旦键合两个原子(例如，N或C)价键则已经满足。相反，当碳是连接原子时，两个另外的化学基团能够附接至该碳原子。合适的化学基团包括但不限于氢、羟基、烷基、烷氧基、＝O、卤素、硝基、胺、酰胺、巯基、芳基、杂芳基、环烷基和杂环基。
本发明使用的术语“环状结构”或类似术语是指任何环状化学结构，其包括但不限于芳基、杂芳基、环烷基、环烯基、杂环基、卡宾和N-杂环卡宾。
本发明使用的术语“取代的”或类似术语包含有机化合物的所有允许的取代基。广义上，允许的取代基包括有机化合物的环状和非环状、支链和非支链、碳环和杂环、芳香族和非芳香族取代基。例如，示例性取代基包括以下所述。对于合适的有机化合物来说，允许的取代基可为一个或多个，相同或不同。对于本发明的目的而言，杂原子(例如氮)能够具有氢取代基和/或本发明所述满足该杂原子价键的有机化合物的任何允许取代基。本发明不意图以任何方式用有机化合物允许的取代基来进行任何限制。同样，术语“取代”或“取代有”包含隐含条件是这种取代符合取代的原子和该取代基的允许的价键，和该取代导致稳定的化合物(例如，不会自发地进行转化(例如通过重排、环化、消去等)的化合物)。在某些方面，除非明确 指出相反，否则，单独的取代基能够进一步任选地取代(即，进一步取代或未取代的)。
在定义各种术语时，“R 1”、“R 2”、“R 3”和“R 4”在本发明中作为通用符号来表示各种特定的取代基。这些符号能够是任何取代基，不限于本发明公开的那些，当它们在一个实例中被定义为某些取代基时，在另一个实例中也可以被定义为一些其他取代基。
本发明使用的术语“烷基”是1至30个碳原子的支链或非支链的饱和烃基，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基、十六烷基、二十烷基、二十四烷基等。该烷基可为环状或非环状。该烷基可为支链或非支链的。该烷基也可为取代或未取代的。例如，该烷基可取代一个或多个基团，包括但不限于本发明所述的任选取代的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。“低级烷基”基团是含有1至6个(例如1至4个)碳原子的烷基。
在整个说明书中，“烷基”通常同时指未取代烷基和取代烷基；但是，取代烷基也在本发明中通过确定烷基上的特定取代基来具体地提及。例如，术语“卤化的烷基”或者“卤代烷基”具体是指取代有一个或多个卤素(例如，氟、氯、溴或碘)的烷基。术语“烷氧基烷基”具体是指取代有一个或多个烷氧基的烷基，如下所述。术语“烷基氨基”具体是指取代有一个或多个氨基的烷基，如下所述等。当在一种情况中使用“烷基”而在另一情况中使用具体的术语如“烷基醇”时，不意味着暗示该术语“烷基”不同时指代具体的术语如“烷基醇”等。
这种做法也用于本发明所述的其它基团。也即，当术语如“环烷基”同时指代未取代的和取代的环烷基部分时，该取代的部分可另外具体地在本发明中确定；例如，具体取代的环烷基可称为例如“烷基环烷基”。类似的，取代的烷氧基可具体地称为例如“卤代烷氧基”，具体的取代烯基可为例如“烯醇”等。同样地，使用通用术语如“环烷基”和具体术语如“烷基环烷基”的不意味着该通用术语不同时包含该具体术语。
本发明使用的术语“环烷基”是由至少三个碳原子构成的3至30个碳原子的非芳香族的碳基环。环烷基的例子包括但不限于环丙基、环丁基、环戊基、环己基、环壬基等。术语“杂环烷基”是一类如上定义的环烷基，并且包含在术语“环烷基”的含义中，其中至少一个环碳原子被杂原子例如但不限于氮、氧、硫或磷取代。该环烷基和杂环烷基可为取代或未取代的。该环烷基和杂环烷基可取代有一个或多个基团，包括但不限于如本发明所述的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。
本发明使用的术语“烷氧基”和“烷氧基基团”是指通过醚键键合的1至30个碳原子的烷基或环烷基；即“烷氧基”可定义为—OR 1，其中R 1是如上定义的烷基或环烷基。“烷氧基”也包含刚刚描述的烷氧基聚合物；即烷氧基可为聚醚，如—OR 1-OR 2或—OR 1-(OR 2) a-OR 3，其中“a”是整数1至500，而R 1、R 2和R 3各自独立地为烷基、环烷基或其组合。
本发明使用的术语“烯基”是2至30个碳原子的烃基，其结构式含有至少一个碳-碳双键。不对称结构如(R 1R 2)C＝C(R 3R 4)包含E和Z异构体。这可推定在本发明的结构式中，其中存在不对称烯烃，或者它可通过键符号C＝C明确表示。该烯基可取代有一个或多个基团，包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环烯基”是非芳香族的3至30个碳原子的碳基环，其由至少3个碳原子构成，并且含有至少一个碳碳双键，即C＝C。环烯基的实例包括但不限于环丙烯基、环丁烯基、环戊烯基、环戊二烯基、环己烯基、环己二烯基、环庚烯基等。术语“杂环烯基”是一类如上定义的环烯基，并且包含在术语“环烯基”的含义中，其中该环的至少一个碳原子用杂原子例如但不限于氮、氧、硫或磷取代。环烯基和杂环 烯基可为取代或未取代的。该环烯基和杂环烯基可取代有一个或多个基团，包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“炔基”是具有2至30个碳原子的烃基，其结构式至少含有一个碳-碳三键。炔基可为未取代的或者取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环炔基”是非芳香族的碳基环，其包含至少7个碳原子并含有至少一个碳-碳三键。环炔基的实例包括但不限于环庚炔基、环辛炔基、环壬炔基等。术语“杂环炔基”是如上所定义的一种环烯基，并且包含在术语“环炔基”的含义内，其中所述环的碳原子中的至少一个被杂原子替代，所述杂原子例如但不限于氮、氧、硫或磷。环炔基和杂环炔基可为取代或未取代的。环炔基和杂环炔基可取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“芳基”是指含有任何碳基芳香族的60个碳原子及以内的基团，包括但不限于苯、萘、苯基、联苯、苯氧基苯等。术语“芳基”也包括“杂芳基”，其被定义为含有芳香族的基团，所述芳香族基团环内至少含有一个杂原子。杂原子的实例包括但不限于氮、氧、硫或磷。同样，术语“非杂芳基”(其也包括在术语“芳基”中)定义了含有芳香族的基团，所述芳香族基团不含杂原子。芳基可为取代或未取代的。芳基可取代有一个或多个基团，所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。术语“联芳基”是特定类型的芳基并且包含在“芳基”的定义中。联芳基是指经稠合的环结构结合在一起的两个芳基，如在萘中一样，或者经一个或多个碳-碳键连接的两个芳基，如在联苯中一样。
本发明使用的术语“醛”通过式—C(O)H表示。在整个说明书中，“C(O)”是羰基(即，C＝O)的简写形式。
本发明使用的术语“胺”或“氨基”通过式—NR 1R 2表示，其中R 1和R 2可以独立的从氢、烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基中选择。
本发明使用的术语“烷基氨基”通过式—NH(-烷基)表示，其中烷基如本发明所述。代表性实例包括但不限于甲基氨基、乙基氨基、丙基氨基、异丙基氨基、丁基氨基、异丁基氨基、仲丁基氨基、叔丁基氨基、戊基氨基、异戊基氨基、叔戊基氨基、己基氨基等。
本发明使用的术语“二烷基氨基”通过式—N(-烷基) 2表示，其中烷基如本发明所述。代表性实例包括但不限于二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、二异丁基氨基、二仲丁基氨基、二叔丁基氨基、二戊基氨基、二异戊基氨基、二叔戊基氨基、二己基氨基、N-乙基-N-甲基氨基、N-甲基-N-丙基氨基、N-乙基-N-丙基氨基等。
本发明使用的术语“羧酸”通过式—C(O)OH表示。
本发明使用的术语“酯”通过式—OC(O)R 1或者—C(O)OR 1表示，其中R 1可为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚酯”通过式—(R 1O(O)C-R 2-C(O)O) a—或者—(R 1O(O)C-R 2-OC(O)) a—表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。术语“聚酯”用于描述通过具有至少两个羧基的化 合物与具有至少两个羟基的化合物之间的反应产生的基团。
本发明使用的术语“醚”通过式R 1OR 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚醚”通过式—(R 1O-R 2O) a—表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。聚醚基团的实例包括聚氧化乙烯、聚氧化丙烯和聚氧化丁烯。
本发明使用的术语“卤素”是指卤素氟、氯、溴和碘。
本发明使用的术语“杂环基”是指单环的和多环的非芳香族环系，并且本发明使用的“杂芳基”是指单环和多环的不多于60个碳原子的芳香族环系：其中环成员中的至少一个不为碳。该术语包括氮杂环丁烷基、二噁烷基、呋喃基、咪唑基、异噻唑基、异噁唑基、吗啉基、噁唑基(包括1,2,3-噁二唑基、1,2,5-噁二唑基和1,3,4-噁二唑基的噁唑基)、哌嗪基、哌啶基、吡嗪基、吡唑基、哒嗪基、吡啶基、嘧啶基、吡咯基、吡咯烷基、四氢呋喃基、四氢吡喃基、包括1,2,4,5-四嗪基的四嗪基、包括1,2,3,4-四唑基和1,2,4,5-四唑基的四唑基、包括1,2,3-噻二唑基、1,2,5-噻二唑基和1,3,4-噻二唑基的噻二唑基、噻唑基、噻吩基、包括1,3,5-三嗪基和1,2,4-三嗪基的三嗪基、包括1,2,3-三唑基和1,3,4-三唑基的三唑基等。
本发明使用的术语“羟基”通过式—OH表示。
本发明使用的术语“酮”通过式R 1C(O)R 2表示，其中R 1和R 2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“硝基”通过式—NO 2表示。
本发明使用的术语“腈”通过式—CN表示。
本发明使用的术语“甲硅烷基”通过式—SiR 1R 2R 3表示，其中R 1、R 2和R 3可独立地为氢或者本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“巯基”通过式—SH表示。
本发明使用的“R 1”、“R 2”、“R 3”、“R n”(其中n为整数)可独立地具有上面列举的基团中的一个或者多个。例如，如果R 1为直链烷基，那么烷基的一个氢原子可任选取代有羟基、烷氧基、烷基、卤素等。取决于选择的基团，第一基团可结合在第二基团内，或者第一基团可侧连(即，连接)至第二基团。例如，对于短语“包含氨基的烷基”，氨基可结合在烷基的主链内。可选择地，氨基可连接至烷基的主链。所选基团的性质将决定是否第一基团嵌入或者连接至第二基团。
本发明所述化合物可含有“任选取代的”部分。通常，术语“取代的”(无论在前面是否存在术语“任选”)意味着指定部分的一个或多个氢被合适的取代基取代。除非另作说明，否则“任选取代的”基团可在基团的每个可取代位置具有合适的取代基，并且当任何给定结构中的一个以上位置可以被选自指定基团的一个以上取代基取代时，取代基可以在每个位置上相同或不同。本发明设想的取代基组合优选为形成稳定的或化学上可行的化合物的组合。还可以设想，在某些方面，除非明确指出相反，各个取代基可进一步任选被取代(即，进一步取代或未取代)。
化合物的结构可通过下式表示：
Figure PCTCN2022088329-appb-000028
其被理解为等同于下式：
Figure PCTCN2022088329-appb-000029
其中n通常为整数。即，R n被理解为表示五个单独的取代基R n(a)、R n(b)、R n(c)、R n(d)、R n(e)。“单独的取代基”是指每个R取代基可独立地限定。例如，如果在一个情况中R n(a)为卤素，那么在这种情况下R n(b)不一定是卤素。
在本发明公开和描述的化学结构和单元中数次提及R 1、R 2、R 3、R 4、R 5、R 6等。在说明书中R 1、R 2、R 3、R 4、R 5、R 6等的任何描述分别适用于引用R 1、R 2、R 3、R 4、R 5、R 6等的任何结构或者单元，除非另作说明。
本发明使用的术语“稠环”是指相邻的两个取代基可以稠合成六元芳环、杂芳环，例如苯环、吡啶环、吡嗪环、哒嗪环、间二氮杂环等，以及饱和的六元或七元碳环或碳杂环等。
由于多种原因，使用有机材料的光电子器件变得越来越迫切。用于制造这种装置的许多材料相对便宜，因此有机光电装置具有无机装置成本优势的潜力。此外，有机材料的固有特性，例如它们的柔性，可以使它们非常适合于诸如在柔性基底上的制造等特殊应用。有机光电子器件的实例包括有机发光器件(OLED)，有机光电晶体管，有机光伏电池和有机光电探测器。对于OLED，有机材料可能具有优于常规材料的性能优点。例如，有机发光层发光的波长通常可以用适当的掺杂剂容易地调谐。
激子从单重激发态衰减到基态以产生即时发光，其是荧光。如果激子从三重激发态衰减到基态以产生发光，这是磷光。由于重金属原子在单线态和三线态激发态之间的强自旋轨道耦合，有效地增强了系间穿越(ISC)，所以磷光金属配合物(如铂配合物)已经表现出其同时利用单线态和三线态激子的潜力，实现100％内部量子效率。因此，磷光金属配合物是有机发光器件(OLED)的发射层中的掺杂剂的良好候选物，并且在学术和工业领域中已经获得了极大的关注。在过去十年中，已经取得了许多成果，从而导致了该技术的有利可图的商业化，例如，OLED已被用于智能手机，电视和数码相机的高级显示器。
然而，迄今为止，蓝色电致发光器件仍然是该技术中最具挑战性的领域，蓝色器件的稳定性是其一大问题。已经证明，主体材料的选择对蓝色器件的稳定性非常重要。但是，蓝色发光材料的三重激发态(T 1)最低能量非常高，这意味着蓝色器件的主体材料的三重激发态(T 1)最低能量应该更高。这导致蓝色设备的主体材料的开发困难加大。
本发明的金属配合物可以被定制或调谐到期望具有特定发射或吸收特性的特定应用。可以通过改变围绕金属中心的配体的结构或改变配体上的荧光发光体的结构来调节本公开中的金属配合物的光学性质。例如，在发射和吸收光谱中，具有给电子取代基的配体的金属配合物或吸电子取代基通常可以表现出不同的光学性质。可以通过修饰荧光发光体和配体上的共轭基团来调节金属配合物的颜色。
这种本发明的配合物的发射可以例如通过改变配体或荧光发光体结构来调节，例如从紫外线到近红外。荧光发光体是有机分子中的一组原子，其可以吸收能量以产生单重态激发态，单重激子迅速衰变以产生即时发光。一方面，本发明的配合物可提供大部分可见光谱的发射。在具体实例中，本发明的配合物可以在约400nm至约700nm的范围内发光。另一方面，本发明的配合物相对于传统的发射配合物具有改进的稳定性和效率。另外，本发明的配合物可用作例如生物应用，抗癌剂，有机发光二极管(OLED)中的发射体或其组合的发光标记。在另一方面，本发明的配合物可用于发光器件，例如紧凑型荧光灯(CFL)，发光二极管(LED)，白炽灯及其组合。
本文公开了包含铂的化合物或复合配合物。术语化合物或配合物在本发明可互换使用。另外，本文公 开的化合物具有中性电荷。
本文公开的化合物可以表现出期望的性质并且具有可以通过选择合适的配体调节的发射和/或吸收光谱。在另一方面，本发明可以排除本文具体叙述的任何一种或多种化合物，结构或其部分。
本文公开的化合物适用于各种各样的光学和电光装置，包括但不限于光吸收装置，例如太阳能和感光装置，有机发光二极管(OLED)，光发射器件或能够兼容光吸收和发射的器件以及用作生物应用的标记物。
如上所述，所公开的化合物是铂配合物。同时，本文公开的化合物可用作OLED应用的主体材料，例如全色显示器。
本文公开的化合物可用于各种应用。作为发光材料，该化合物可用于有机发光二极管(OLED)，发光装置和显示器以及其他发光器件。
本发明的化合物可以使用多种方法制备，包括但不限于本文提供的实施例中所述的那些。
本文公开的化合物可以是延迟的荧光和/或磷光发射体。一方面，本文公开的化合物可以是延迟的荧光发射体。一方面，本文公开的化合物可以是磷光发射体。另一方面，本文公开的化合物可以是延迟荧光发射体和磷光发射体。
本公开涉及环金属铂配合物，其可用作OLED器件中发光材料和主体材料。
除非另有说明，以下试验中所涉及到的所有商业试剂购买后直接使用，没有进一步纯化。核磁共振氢谱和碳谱均在氘代氯仿(CDCl 3)或氘代二甲基亚砜(DMSO-d 6)溶液中测得，氢谱使用400或500兆赫兹的核磁共振谱仪，碳谱使用100或126兆赫兹的核磁共振谱仪，化学位移以四甲基硅烷(TMS)或残留溶剂为基准。如果用CDCl 3作溶剂，则氢谱和碳谱分别以TMS(δ＝0.00ppm)和CDCl 3(δ＝77.00ppm)作为内标。如果用DMSO-d 6作溶剂，则氢谱和碳谱分别以TMS(δ＝0.00ppm)和DMSO-d 6(δ＝39.52ppm)作为内标。以下缩写(或组合)用于解释氢谱峰：s＝单峰，d＝双重峰，t＝三重峰，q＝四重峰，p＝五重峰，m＝多重峰，br＝宽峰。高分辨质谱在Applied Biosystems公司的ESI-QTOF质谱仪上测得，样品电离模式为电喷雾电离。
实施例1：四齿环金属铂(II)配合物磷光发光材料PtDMCz合成路线如下：
Figure PCTCN2022088329-appb-000030
中间体3的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物1(1.00g,5.31mmol,1.0当量)，化合物2(2.07g,6.38mmol,1.2当量)，碘化亚铜(51mg,0.27mmol,5mol％)，2-甲酸吡啶(65mg,0.53mmol,10mol％)，磷酸钾(2.26g,10.62mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在90℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入少量的盐水，并用乙酸乙酯萃取。有机层用水洗涤两次，水层用乙酸乙酯萃取两次。合并有机相，无水 硫酸钠干燥，过滤。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/乙酸乙酯＝10:1-3:1-2:1，得到中间体3，粘稠液体1.80g，收率88％。 1H NMR(DMSO-d 6,400MHz):δ2.15(s,3H),2.30(s,3H),6.06(s,1H),7.07(dd,J＝8.0,2.4Hz,1H),7.13-7.16(m,3H),7.30-7.32(m,1H),7.36-7.40(m,2H),7.52(t,J＝8.0,1H),7.57(dd,J＝7.6,1.2Hz,1H),7.59-7.64(m,1H),7.75(td,J＝7.6,1.2Hz,1H),7.97(dd,J＝8.0,1.2Hz,1H)。
中间体4的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物3(1.71g,4.41mmol,1.0当量)，三苯基膦(3.47g,13.23mmol,3.0当量)，然后抽换氮气三次，在氮气保护下加入邻二氯苯(25mL)。该混合物在180℃油浴中搅拌反应24小时，薄层色谱监测至原料反应完毕，冷却至室温。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-5:1，得到中间体4，白色固体1.43g，收率92％。 1H NMR(500MHz,CDCl 3):δ2.26(s,3H),2.27(s,3H),5.96(s,1H),6.81(d,J＝2.0Hz,1H),6.92(dd,J＝8.5,2.0Hz,1H),6.97-7.00(m,1H),7.07(t,J＝2.0Hz,1H),7.14-7.16(m,1H),7.21-7.25(m,1H),7.31-7.37(m,3H),7.96(d,J＝8.5Hz,1H),8.01(d,J＝7.5Hz,1H),8.53(s,1H)。
配体1的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物4(1.00g,2.83mmol,1.0当量)，化合物5(955mg,3.11mmol,1.1当量)，三(二亚苄基丙酮)二钯(104mg,0.11mmol,4mol％)，配体JohnPhos(68mg,0.23mmol,8mol％)，叔丁醇钠(544mg,5.66mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入甲苯(30mL)和二氧六环(30mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。过滤，并用乙酸乙酯淋洗，滤液用水洗涤两次，水层用乙酸乙酯萃取两次。合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-1:1，得到配体1，泡沫状固体1.50g，收率85％。HRMS(ESI):C 42H 34N 5O[M+H] +的计算值为624.2758，实测值为624.2761。 1H NMR(500MHz,CDCl 3):δ2.05(s,6H),2.23(s,3H),2.24(s,3H),5.93(s,1H),6.99-7.01(m,1H),7.06(dd,J＝8.5,2.0Hz,1H),7.10-7.15(m,4H),7.19(t,J＝7.5Hz,2H),7.29-7.35(m,2H),7.38(td,J＝7.5,1.5Hz,1H),7.43(dd,J＝5.0,1.5Hz,1H),7.67(d,J＝2.5Hz,1H),7.75(d,J＝8.0Hz,1H),7.81(d,J＝2.0Hz,1H),7.98(d,J＝7.5Hz,2H),8.04(d,J＝8.5Hz,2H),8.78(d,J＝5.0Hz,1H)。 13C NMR(125MHz,CDCl 3):δ12.40,13.39,19.65,102.73,107.16,110.77,113.65,114.58,116.80,118.17,118.95,119.93,120.75,120.77,120.99,121.11,121.14,121.63,123.95,124.31,124.61,125.91,129.34,129.87,139.21,139.61,140.38,140.41,141.16,148.99,149.74,152.28,153.08,155.66,158.2。
PtDMCz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体1(624mg,1.00mmol,1.0当量)，亚氯铂酸钾(457mg,1.10mmol,1.1当量)，四丁基溴化铵(32mg,0.10mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(60mL)，氮气鼓泡25分钟。该混合物在室温下搅拌8小时，再在110℃的油浴锅中搅拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-5:1，得到Pt1，黄色固体595mg，收率73％。HRMS(ESI):C 42H 32N 5O 195Pt[M+H] +的计算值为817.2249，实测值为817.2236。 1H NMR(500MHz,DMSO-d 6):δ2.06(s,6H),2.47(s,3H),2.75(s,3H),6.45(s,1H),6.99(dd,J＝8.0,1.0Hz,1H),7.15-7.26(m,6H),7.30-7.36(m,3H),7.53(dd,J＝8.5,2.0Hz,1H),7.87(d,J＝8.0Hz,1H),7.90-7.93(m,1H),8.09-8.14(m,3H),8.43(d,J＝2.0Hz,1H),9.40(d,J＝6.5Hz,1H)。 13C NMR(125MHz,CDCl 3):δ14.44,15.84,19.90,99.56,106.99,110.05,110.32,113.28,113.40,114.32,115.51,116.40,117.59,118.33,120.11,120.53,120.94,120.96,123.37,124.26,124.67,124.84,129.48,137.94,139.85,141.39,142.01,147.76,148.98,149.24,152.63,152.68,152.90,153.91。
实施例2：四齿环金属铂(II)配合物磷光发光材料PtDMCz-2-ptz合成路线如下：
Figure PCTCN2022088329-appb-000031
配体DMCz-2-ptz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量)，化合物5(246mg,1.10mmol,1.1当量)，碘化亚铜(19mg,0.10mmol,10mol％)，2-吡啶甲酸(25mg,0.20mmol,20mol％)，磷酸钾(425mg,2.00mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到配体DMCz-2-ptz，泡沫状固体518mg，收率87％。 1H NMR(500MHz,CDCl 3):δ2.01(s,6H),7.02(ddd,J＝8.0,3.0,1.0Hz,1H),7.07(d,J＝7.5Hz,2H),7.10(dd,J＝8.5,2.0Hz,1H),7.18(t,J＝7.5Hz,2H),7.32-7.38(m,2H),7.39-7.43(m,2H),7.63(d,J＝2.5Hz,1H),7.66(s,2H),7.71(ddd,J＝7.5,2.5,1.0Hz,1H),7.78(t,J＝2.0Hz,1H),7.82-7.84(m,2H),7.96(d,J＝7.5Hz,2H),8.06-8.08(m,2H),8.78(d,J＝5.5Hz,1H)。 13C NMR(125MHz,CDCl 3):δ19.61,102.27,109.23,111.04,113.47,113.67,114.74,115.21,117.41,118.17,119.93,120.73,121.08,121.33,121.70,123.97,124.59,125.98,129.32,130.35,135.46,139.74,140.36,140.90,149.76,149.93,152.12,152.34,153.15,155.71,158.51,164.75。
PtDMCz-2-ptz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-2-ptz(200mg,0.34mmol,1.0当量)，亚氯铂酸钾(153mg,0.37mmol,1.1当量)，四丁基溴化铵(10mg,0.03mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(20mL)，氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-2-ptz，黄色固体102mg，收率39％。 1H NMR(500MHz,DMSO-d 6):δ2.15(s,6H),7.16-7.23(m,5H),7.30-7.37(m,4H),7.57(dd,J＝8.0,1.5Hz,1H),7.60(dd,J＝6.0,2.0Hz,1H),7.90-7.91(m,1H),7.97(d,J＝8.5Hz,1H),8.11(dd,J＝8.5,1.0Hz,2H),8.15-8.17(m,1H),8.50(d,J＝0.5Hz,1H),8.54(d,J＝2.0Hz,1H),8.79(d,J＝0.5Hz,1H),9.44(d,J＝6.0Hz,1H)。
实施例3：四齿环金属铂(II)配合物磷光发光材料PtDMCz-1-ptz合成路线如下：
Figure PCTCN2022088329-appb-000032
配体DMCz-1-ptz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量)，化合物7(246mg,1.10mmol,1.1当量)，碘化亚铜(19mg,0.10mmol,10mol％)，2-吡啶甲酸(25mg,0.20mmol,20mol％)，磷酸钾(425mg,2.00mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完 毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到配体DMCz-1-ptz，泡沫状固体509mg，收率85％。 1H NMR(500MHz,CDCl 3):δ2.03(s,6H),7.08-7.10(m,4H),7.19(t,J＝2.5Hz,2H),7.34(t,J＝2.5Hz,1H),7.39-7.45(m,5H),7.64(d,J＝2.0Hz,1H),7.76(d,J＝1.0Hz,1H),7.80-7.84(m,3H),7.98(d,J＝7.5Hz,2H),8.08(t,J＝7.5Hz,2H),8.79(d,J＝5.0Hz,1H)。 13C NMR(125MHz,CDCl 3):δ19.67,102.73,110.60,111.03,113.76,114.82,118.23,118.26,120.04,120.83,120.99,121.12,121.22,121.43,121.59,121.82,124.04,124.27,124.64,126.17,129.39,130.83,134.36,138.11,139.72,140.32,140.41,149.81,152.31,153.17,155.21,159.04。
PtDMCz-1-ptz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-1-ptz(100mg,0.17mmol,1.0当量)，亚氯铂酸钾(77mg,0.18mmol,1.1当量)，四丁基溴化铵(6mg,0.02mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(10mL)，氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-1-ptz，黄色固体41mg，收率31％。 1H NMR(500MHz,DMSO-d 6):δ2.15(s,6H),7.04-7.08(m,5H),7.29-7.34(m,3H),7.39(t,J＝8.0Hz,1H),7.76(d,J＝7.5Hz,1H),7.80-7.82(m,1H),7.91(dd,J＝6.0,2.0Hz,1H),7.99(d,J＝8.5Hz,1H),8.11(dd,J＝7.0,1.0Hz,2H),8.15-8.18(m,1H),8.43(dd,J＝2.0,1.0Hz,1H),8.46(d,J＝0.5Hz,1H),9.44(d,J＝1.5Hz,1H),10.36(d,J＝6.0Hz,1H)。
实施例4：四齿环金属铂(II)配合物磷光发光材料PtDMCz-piz合成路线如下：
Figure PCTCN2022088329-appb-000033
配体DMCz-piz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(363mg,0.80mmol,1.0当量)，化合物8(228mg,0.96mmol,1.1当量)，碘化亚铜(15mg,0.08mmol,10mol％)，2-吡啶甲酸(20mg,0.16mmol,20mol％)，磷酸钾(340mg,1.60mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(16mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到配体DMCz-piz，泡沫状固体268mg，收率81％。 1H NMR(500MHz,CDCl 3):δ1.97(s,6H),3.58(s,3H),6.87(s,1H),7.00(dd,J＝8.5,2.0Hz,1H),7.04(d,J＝7.0Hz,2H),7.06-7.08(m,1H),7.10-7.13(m,3H),7.22(s,1H),7.24-7.27(m,1H),7.32(dd,J＝8.5,1.5Hz,1H),7.35(d,J＝5.0Hz,2H),7.37(dd,J＝5.0,1.5Hz,1H),7.57(d,J＝2.0Hz,1H),7.71(d,J＝8.5Hz,1H),7.75(d,J＝1.5Hz,1H),7.91(d,J＝7.5Hz,2H),7.99(dd,J＝7.5,1.5Hz,2H),8.72(d,J＝5.0Hz,1H)。 13C NMR(125MHz,CDCl 3):δ19.64,34.40,102.37,110.88,113.53,118.14,118.50,118.72,119.89,120.65,120.74,120.98,121.13,121.18,121.65,122.46,123.36,123.94,124.35,124.58,125.89,128.18,129.36,129.87,131.97,139.63,140.36,140.37,149.75,152.31,153.07,156.02,157.77。
PtDMCz-piz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-piz(94mg,0.15mmol,1.0当量)，亚氯铂酸钾(70mg,0.17mmol,1.1当量)，四丁基溴化铵(6mg,0.02mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(10mL)，氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅 拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-piz，黄色固体69mg，收率56％。 1H NMR(500MHz,DMSO-d 6):δ2.14(s,6H),4.13(s,3H),7.08(dd,J＝8.0Hz,1H),7.17-7.23(m,4H),7.24(d,J＝8.5Hz,1H),7.27(t,J＝7.5Hz,1H),7.32-7.34(m,2H),7.59(d,J＝1.0Hz,1H),7.61(dd,J＝6.5,2.0Hz,1H),7.63-7.65(m,2H),7.86(d,J＝8.0Hz,1H),8.09-8.12(m,4H),8.46(d,J＝2.0Hz,1H),9.42(d,J＝6.0Hz,1H)。
实施例5：四齿环金属铂(II)配合物磷光发光材料PtDMCz-ppy合成路线如下：
Figure PCTCN2022088329-appb-000034
配体DMCz-ppy的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量)，化合物9(258mg,1.10mmol,1.1当量)，碘化亚铜(19mg,0.10mmol,10mol％)，2-吡啶甲酸(25mg,0.20mmol,20mol％)，磷酸钾(425mg,2.00mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到配体DMCz-ppy，泡沫状固体490mg，收率81％。 1H NMR(500MHz,CDCl 3):δ1.91(s,6H),6.99(d,J＝7.0Hz,2H),7.03(d,J＝2.5Hz,1H),7.05(d,J＝1.5Hz,1H),7.07-7.14(m,3H),7.24-7.27(m,1H),7.28(dd,J＝5.0,1.5Hz,1H),7.30-7.34(m,2H),7.46(d,J＝7.5Hz,1H),7.52(d,J＝2.0Hz,1H),7.57(t,J＝6.5Hz,2H),7.65(t,J＝2.0Hz,1H),7.75-7.78(m,2H),7.87(d,J＝7.5Hz,2H),7.98(d,J＝8.0Hz,2H),8.48(d,J＝4.0Hz,1H),8.68(d,J＝5.0Hz,1H)。
PtDMCz-ppy的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-ppy(100mg,0.16mmol,1.0当量)，亚氯铂酸钾(75mg,0.18mmol,1.1当量)，四丁基溴化铵(6mg,0.02mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(10mL)，氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-ppy，黄色固体54mg，收率41％。 1H NMR(500MHz,CDCl 3):δ2.10(s,6H),7.08(d,J＝7.0Hz,2H),7.15(d,J＝7.5Hz,2H),7.18(d,J＝2.0Hz,1H),7.20-7.26(m,4H),7.32-7.36(m,2H),7.55(dd,J＝5.0,3.0Hz,1H),7.68(d,J＝8.0Hz,1H),7.73(d,J＝8.0Hz,1H),7.87-7.90(m,1H),7.93(d,J＝7.5Hz,4H),8.36(d,J＝1.5Hz,1H),8.64(d,J＝5.5Hz,1H),9.11(d,J＝6.0Hz,1H)。
实施例6：四齿环金属铂(II)配合物磷光发光材料PtDMCz-NHC合成路线如下：
Figure PCTCN2022088329-appb-000035
中间体11的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(676mg,1.49mmol,1.0当量)，化合物10(500mg,1.79mmol,1.2当量)，碘化亚铜(29mg,0.15mmol,10mol％)，2-吡啶甲酸(37mg,0.30mmol,20mol％)，磷酸钾(633mg,2.98mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到中间体11，泡沫状固体801mg，收率82％。 1H NMR(500MHz,CDCl 3):δ1.28(s,9H),2.05(s,6H),6.39(t,J＝7.5Hz,1H),6.87(s,1H),7.07(d,J＝2.0Hz,1H),7.09(d,J＝1.5Hz,1H),7.10-7.12(m,2H),7.14(s,1H),7.20(t,J＝7.5Hz,2H),7.23-7.27(m,1H),7.32-7.35(m,1H),7.40(dd,J＝8.5,2.0Hz,1H),7.42-7.44(m,2H),7.69(d,J＝2.0Hz,1H),7.79(d,J＝8.5Hz,1H),7.83(d,J＝2.0Hz,1H),7.99(d,J＝2.5Hz,2H),8.08(t,J＝6.5Hz,2H),8.78(d,J＝5.0Hz,1H)。
配体DMCz-NHC的合成：向带有磁力搅转子干燥封管中加入中间体11(800mg,1.23mmol,1.0当量)，然后抽换氮气三次，在氮气保护下加入甲苯(40mL)和碘甲烷(210mg,1.48mmol,1.2当量)。该混合物在100℃的油浴锅中搅拌反应2天，冷却至室温，过滤，滤液用石油醚淋洗，干燥，所得灰色固体加入到甲醇/水(40mL/4mL)中，搅拌溶解后加入六氟磷酸铵(302mg,1.85mmol,1.5当量)，室温搅拌反应3天。加入水，减压蒸去大部分甲醇，过滤，先水洗后石油醚洗，干燥，得到配体DMCz-NHC，灰色固体810mg，收率81％。 1H NMR(500MHz,DMSO-d 6):δ1.23(s,9H),2.15(s,6H),3.32(s,3H),6.93(t,J＝2.5Hz,1H),7.01(dd,J＝8.0,0.5Hz,1H),7.18-7.27(m,6H),7.33-7.37(m,2H),7.54(dd,J＝7.5,0.5Hz,1H),7.60(dd,J＝6.0,2.0Hz,1H),7.88-7.91(m,2H),8.09-8.11(m,2H),8.13-8.14(m,1H),8.31(d,J＝2.0Hz,1H),8.50(d,J＝2.0Hz,1H),8.93(d,J＝2.5Hz,1H),9.42(d,J＝6.5Hz,1H),11.94(s,1H)。
PtDMCz-NHC的合成：向带有磁力搅转子的封管中依次加入配体DMCz-NHC(200mg,0.25mmol,1.0当量)，(1,5-环辛二烯)二氯化铂(97mg,0.26mmol,1.05当量)和醋酸钠(61mg,0.74mmol,3.0当量)，然后抽换氮气三次，在氮气保护下加入二乙二醇二甲醚(20mL)，鼓氮气30分钟。该混合物避光条件下在120℃的油浴锅中搅拌反应3天，冷却至室温，加入蒸馏水淬灭反应，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-NHC，黄色固体71mg，收率34％。 1H NMR(500MHz,DMSO-d 6):δ1.43(s,9H),2.15(s,6H),4.11(s,3H),6.99(d,J＝2.5Hz,1H),7.25-7.30(m,4H),7.37-7.40(m,3H),7.42(d,J＝2.0Hz,1H),7.54(d,J＝2.5Hz,1H),7.58(dd,J＝6.0,1.5Hz,1H),7.93-7.96(m,2H),8.15-8.18(m,3H),8.30(d,J＝2.0Hz,1H),8.43(d,J＝2.5Hz,1H),9.75(d,J＝6.0Hz,1H)。
实施例7：四齿环金属铂(II)配合物磷光发光材料PtDMCz-Ph-NHC合成路线如下：
Figure PCTCN2022088329-appb-000036
中间体13的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(1.80g,3.97mmol,1.0当量)，化合物12(1.44g,4.37mmol,1.1当量)，碘化亚铜(76mg,0.40mmol,10mol％)，2-吡啶甲酸(97mg,0.79mmol,20mol％)，磷酸钾(1.69g,7.94mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(60mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到中间体13，泡沫状固体2.25g，收率81％。 1H NMR(500MHz,CDCl 3):δ1.32(s,9H),2.06(s,6H),7.00(s,1H),7.09-7.12(m,3H),7.17-7.21(m,4H),7.26-7.36(m,6H),7.40(td,J＝8.5,1.5Hz,1H),7.43(dd,J＝5.0,1.5Hz,1H),7.75-7.77(m,2H),7.85(d,J＝1.0Hz,1H),7.98(d,J＝7.5Hz,2H),8.07(d,J＝7.0Hz,1H),8.09(d,J＝8.5Hz,1H),8.79(d,J＝5.0Hz,1H)。
配体DMCz-Ph-NHC的合成：向带有磁力搅转子干燥封管中加入中间体13(400mg,0.57mmol,1.0当量)，然后抽换氮气三次，在氮气保护下加入甲苯(40mL)和碘甲烷(97mg,0.68mmol,1.2当量)。该混合物在100℃的油浴锅中搅拌反应2天，冷却至室温，过滤，滤液用石油醚淋洗，干燥，所得灰色固体加入到甲醇/水(40mL/4mL)中，搅拌溶解后加入六氟磷酸铵(140mg,0.86mmol，1.5当量)，室温搅拌反应3天。加入水，减压蒸去大部分甲醇，过滤，先水洗后石油醚洗，干燥，得到配体DMCz-Ph-NHC，灰色固体364mg，收率74％。 1H NMR(500MHz,CDCl 3):δ1.36(s,9H),2.07(s,6H),4.20(s,3H),7.03(t,J＝2.5Hz,1H),7.11-7.14(m,3H),7.19(t,J＝2.5Hz,2H),7.30-7.33(m,1H),7.37-7.40(m,2H),7.45-7.47(m,2H),7.54-7.58(m,1H),7.63-7.66(m,2H),7.70-7.75(m,3H),7.83(d,J＝1.5Hz,1H),7.97(d,J＝7.5Hz,2H),8.05(d,J＝7.5Hz,1H),8.11(d,J＝8.5Hz,1H),8.81(d,J＝5.0Hz,1H),9.34(s,1H)。 13C NMR(125MHz,CDCl 3):δ19.71,30.95,33.77,35.49,102.95,110.73,110.84,113.22,113.30,113.75,116.76,117.77,118.26,120.15,120.90,120.99,121.13,121.35,121.64,121.82,124.17,124.23,124.66,126.19,127.70,127.88,129.42,131.17, 132.03,133.33,139.60,140.43,140.45,140.86,149.98,152.22,153.21,154.70,157.05,159.15。
PtDMCz-Ph-NHC的合成：向带有磁力搅转子的封管中依次加入配体DMCz-Ph-NHC(100mg,0.12mmol,1.0当量)，(1,5-环辛二烯)二氯化铂(49mg,0.13mmol,1.05当量)和醋酸钠(48mg,0.35mmol,3.0当量)，然后抽换氮气三次，在氮气保护下加入二乙二醇二甲醚(10mL)，鼓氮气30分钟。该混合物避光条件下在120℃的油浴锅中搅拌反应3天，冷却至室温，加入蒸馏水淬灭反应，减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯，淋洗剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-Ph-NHC，黄色固体82mg，收率77％。 1H NMR(500MHz,DMSO-d 6):δ1.47(s,9H),2.11(s,6H),4.14(s,3H),7.03(d,J＝1.5Hz,1H),7.18-7.22(m,4H),7.32-7.35(m,3H),7.51-7.52(m,1H),7.54(t,J＝7.5Hz,2H),7.64(d,J＝1.5Hz,1H),7.82(d,J＝8.0Hz,1H),7.92(d,J＝8.0Hz,2H),8.10-8.14(m,3H),8.30(d,J＝8.0Hz,1H),8.48(d,J＝2.0Hz,1H),9.77(d,J＝6.0Hz,1H)。
实施例8：四齿环金属铂(II)配合物磷光发光材料PtDMCz-ppz合成路线如下：
Figure PCTCN2022088329-appb-000037
配体DMCz-ppz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量)，化合物14(245mg,1.10mmol,1.1当量)，碘化亚铜(19mg,0.10mmol,10mol％)，2-吡啶甲酸(25mg,0.20mmol,20mol％)，磷酸钾(425mg,2.00mmol,2.0当量)，然后抽换氮气三次，在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天，薄层色谱监测至原料反应完毕，冷却至室温。加入乙酸乙酯，水洗涤两次，水层用乙酸乙酯萃取两次，合并有机相，无水硫酸钠干燥。减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到配体DMCz-ppz，泡沫状固体506mg，收率85％。 1H NMR(500MHz,CDCl 3):δ2.02(s,6H),6.37(dd,J＝2.5,2.0Hz,1H),6.93-6.95(m,1H),7.07-7.09(m,3H),7.18(d,J＝7.5Hz,2H),7.30-7.35(m,4H),7.38-7.40(m,1H),7.41-7.43(m,2H),7.62(t,J＝1.5Hz,1H),7.78-7.82(m,3H),7.97(d,J＝8.0Hz,2H),8.06(d,J＝8.0Hz,2H),8.78(dd,J＝5.5,0.5Hz,1H)。 13C NMR(125MHz,CDCl 3):δ19.65,102.38,107.65,109.49,110.99,113.51,113.65,116.22,118.20,119.95,120.76,120.82,121.06,121.14,121.29,121.72,123.98,124.36,124.65,125.98,126.66,129.36,130.43,139.71,140.33,140.42,141.09,141.40,149.77,152.35,153.15,155.81,158.68。
PtDMCz-ppz的合成：向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-ppz(100mg,0.17mmol,1.0当量)，亚氯铂酸钾(77mg,0.18mmol,1.1当量)，四丁基溴化铵(6mg,0.02mmol,10mol％)，然后抽换氮气三次，在氮气保护下加入醋酸(15mL)，氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天，冷却至室温。然后减压蒸馏除去溶剂，所得粗品用硅胶层析柱分离提纯，洗脱剂：石油醚/二氯甲烷＝10:1-3:1，得到PtDMCz-ppz，黄色固体65mg，收率49％。 1H NMR(500MHz,DMSO-d 6):δ2.10(s,6H),6.63(t,J＝2.5Hz,1H),7.05-7.11(m,4H),7.15-7.18(m,4H),7.22-7.26(m,2H),7.33(d,J＝8.5Hz,1H),7.66(d,J＝8.5Hz,1H),7.73(d,J＝8.5Hz,1H),7.81(d,J＝2.0Hz,1H),7.90-7.94(m,3H),8.05(d,J＝2.5Hz,1H),8.36(d,J＝2.0Hz,1H),9.33(d,J＝6.5Hz,1H)。
电化学、光物理测试和理论计算说明：
吸收光谱在Agilent 8453紫外-可见光光谱仪上测量，使用Horiba Jobin Yvon FluoroLog-3光谱仪上进行稳态发射实验和寿命测量。低温(77K)发射光谱和寿命在用液氮冷却的2-甲基四氢呋喃溶液中测量。Pd(II)配合物使用Gaussian 09软件包进行理论计算，利用密度泛函理论(DFT)优化了基态(S 0)分子的几何结构，使用B3LYP泛函进行DFT计算，其中C、H、O和N原子使用6-31G(d)基组，Pd原子使用LANL2DZ基组。光稳定性测试条件为5％的发光材料:聚苯乙烯薄膜在375nm紫外光激发下(光强：500W/m2)的发光强度衰减。
实验数据及分析：
为了证明咔唑1,8-位引入取代基的必要性，我们将Pt-DMCz与文献中已报道的Pt1(J.Pgys.Chem.Lett,2018,9,2285)、PtON1(Inorg.Chem.,2017,56,8244)、PtON1-Ph(Inorg.Chem.,2017,56,8244)和PtON1-Cz(Inorg.Chem.,2017,56,8244)做了进一步比较，其结构式如下所示，其光物理性质数据如下表1所示。
Figure PCTCN2022088329-appb-000038
表1：四齿环金属铂(II)配合物发光材料光物理性质数据列表
Figure PCTCN2022088329-appb-000039
注： a为了便于比较，取基于优化后的S 0态在B3LYP/6-31G(d)/LANL2DZ水平下的理论计算值。λ为发射波长；τ obs为材料激发态寿命；Φ PL为磷光量子效率；k r obs为辐射速率；其中k r obs＝Φ PL/τ obs。
表2：四齿环金属铂(II)配合物发光材料光理论计算实验数据
Figure PCTCN2022088329-appb-000040
Figure PCTCN2022088329-appb-000041
Figure PCTCN2022088329-appb-000042
Figure PCTCN2022088329-appb-000043
注：二面角为吡啶环和其4位咔唑环之间的角度。
由附图1可知，通过理论计算优化结构后的PtON1-Cz和PtDMCz中(取代)咔唑/吡啶之间的二面角分别为51 o和88 o，表明在PtDMCz中咔唑的1,8-位引入甲基可以大大增加取代咔唑/吡啶之间的二面角。二面角的增加，可提高分子刚性，有效减少由于分子中咔唑环振动和转动所消耗的能量，减少非辐射衰减，提高材料分子的辐射跃迁速率。
此外，表2中大量理论计算实验数据也说明在咔唑的1,8-位引入取代基可大大增加咔唑/吡啶之间的二面角，均比对照物PtON1-Cz的二面角大，同时也说明1,8-位基团位阻的重要性，为本申请的关键。同时，上述大量的合成实验实施例及其光物理性质表征(表1)和后续的器件测试亦说明了本申请发光材料分子设计的方法是完全成功的。
由附图2和附图3中PtON1-Cz和PtDMCz的低温发射光谱可知，PtON1-Cz为具有精细振动结构的谱图，为典型的电荷转移态(CT)发光；而PtDMCz则为光滑且缺少振动峰的光谱，表明其发光中的金属到配体电荷转移态(MLCT)大大增加，进而使其激发态寿命缩短，由表一和附图4中的实验数据可知，PtDMCz在室温下二氯甲烷溶液中的激发态寿命缩短至1.1微秒(μs)；同时由于取代咔唑环和吡啶环之间的二面角增加，可提高分子刚性，有效减少由于分子中咔唑环振动和转动所消耗的能量，减少非辐射衰减，提高磷光量子效率至88％。以上两个方面的因素使PtDMCz的辐射跃迁速率(k r obs＝Φ PL/τ obs)大大提高。由表一中实验数据可知PtDMCz的辐射跃迁速率k r obs是其同系物发光材料的Pt1、PtON1、PtON1-Ph和PtON1-Cz的2.72-4.91倍。
从图5中PtDMCz、PtDMCz-ppz、PtDMCz-2-ptz、PtDMCz-1-ptz、PtDMCz-piz、PtDMCz-ppy、PtDMCz-NHC和PtDMCz-Ph-NHC在室温下二氯甲烷溶液中的发射光谱图比较可知，通过对杂环结构的调控可以对其光物理性质，如发射光谱图的半峰宽和发射波长进行有效调控。其中PtDMCz-1-ptz在此条件下的绝对量子效率可高达98％。且上述各材料分子的辐射跃迁速率(k r obs＝Φ PL/τ obs)均在8×10 5s -1量级左右，远高于对比材料分子的辐射跃迁速率。
从图6中PtDMCz和PdDMCz的光稳定性测试比较中可看出，PtDMCz比其对应的钯(II)配合物PdDMCz具有明显的稳定性提升。
以上实验数据和理论计算结果充分表明，本发明中发展的基于基于1,8-取代咔唑的四齿环金属铂(II)配合物发光材料具有激发态寿命短、辐射跃迁速率大、磷光量子效率高的特点，使其在OLED领域有着巨大的应用前景。
在有机发光元件中，从正负两电极向发光材料中注入载子，产生激发态的发光材料并使其发光。通过通式(1)代表的本发明的络合物可作为磷光发光材料应用于有机光致发光元件或有机电致发光元件等优异的有机发光元件。有机光致发光元件具有在衬底上至少形成了发光层的结构。另外，有机电致发光元件具有至少形成了阳极、阴极、及阳极和阴极之间的有机层的结构。有机层至少包含发光层，可以仅由发光层构成，也可以除发光层以外具有1层以上的有机层。作为这种其它有机层，可以列举空穴传输层、空穴注 入层、电子阻挡层、空穴阻挡层、电子注入层、电子传输层、激子阻挡层等。空穴传输层也可以是具有空穴注入功能的空穴注入传输层，电子传输层也可以是具有电子注入功能的电子注入传输层。具体的有机发光元件的结构示意如图7所示。在图7中，从下到上共7层，依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极，其中发光层为客体材料掺杂入主体材料的混合层。
本发明的磷光发光材料作为客体材料掺杂入主体材料制成发光层可应用于OLED器件，结构表示为：
ITO/HATCN(10nm)/TAPC(65nm)/mCBP:实施例中所表示的化合物(4-20wt.％,20nm)/PPT(2nm)/Li 2CO 3:Bepp 2(5％,30nm)/Li 2CO 3(1nm)/Al(100nm)
其中，ITO为透明阳极；HATCN是空穴注入层，TAPC是空穴传输层，mCBP是主体材料，所表示的化合物(4-20wt.％是掺杂浓度,20nm是发光层的厚度)是客体材料，PPT是空穴阻隔层，Li 2CO 3:Bepp 2为电子传输层，Li 2CO 3为电子注入层，Al为阴极。括号中单位为纳米(nm)的数字为薄膜的厚度。
在上述器件结构未经优化的情况下，以PtDMCz作为掺杂发光材料的OLED器件外量子效率(EQE)可达20％以上，且具有较小的效率滚降，明显优于相同器件结构中对比掺杂发光材料PtON1-Cz的器件性能。相信通过器件结构的优化和主体材料的改进，其器件性能会进一步提高。
需要说明的是，所述结构为本发明发光材料的一个应用的举例，不构成本发明所示发光材料的具体OLED器件结构的限定，磷光发光材料也不限于实施例中所表示的化合物。
器件中应用材料的分子式如下：
Figure PCTCN2022088329-appb-000044
本发明的有机发光器件的各层可采用真空蒸镀、溅射、离子电镀等方法，或湿法成膜如旋涂、打印、印刷等方法形成，所用的溶剂没有特别限制。
在本发明的另一种优选实施方式中，本发明的OLED器件中含有空穴传输层，空穴传输材料可以优选自已知或未知的材料，特别优选地选自以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022088329-appb-000045
Figure PCTCN2022088329-appb-000046
在本发明的一种优选实施方式中，本发明的OLED器件中含有的空穴传输层，其包含一种或多种p型掺杂剂。本发明优选的p型掺杂剂为以下结构，但并不代表本发明限于以下结构：
Figure PCTCN2022088329-appb-000047
本发明的一种优选实施方式中，所述的电子传输层可以选自化合物ET-1至ET-13的至少一种，但并不代表本发明限于以下结构：
Figure PCTCN2022088329-appb-000048
Figure PCTCN2022088329-appb-000049
电子传输层可以有机材料与一种或多种n型掺杂剂(如LiQ)共同形成。
将实施例1中所表示的化合物作为圆偏振光发光材料应用于OLED器件，结构表示为：在含有ITO的玻璃上，空穴注入层(HIL)为HT-1:P-3(95:5v/v％)，厚度为10纳米；空穴传输层(HTL)为HT-1，厚度为90纳米；电子阻挡层(EBL)为HT-10，厚度为10纳米，发光层(EML)为主体材料(H-1或H-2或H-3或H-4或H-5或H-6):本发明铂金属配合物(95:5v/v％)，厚度为35纳米，电子传输层(ETL)为ET-13：LiQ(50:50v/v％)，厚度为35纳米，然后蒸镀阴极Al为70纳米。
Figure PCTCN2022088329-appb-000050
表3
Figure PCTCN2022088329-appb-000051
Figure PCTCN2022088329-appb-000052
由上述器件数据可知，本申请中高辐射速率掺杂的器件在外量子效率EQE方面均有明显的性能提升。此外，与对比器件相比，器件1至器件8的效率滚降也均大为减小。
本领域的普通技术人员可以理解，上述各实施方式是实现本发明的具体实施例，而在实际应用中，可以在形式上和细节上对其作各种改变，而不偏离本发明的精神和范围。例如，在不背离本发明的精神的情况下，这里描述的许多取代基结构可以用其它结构代替。

Claims (8)

  1. 一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料，其特征在于，是含有1,8-双取代咔唑的四齿环金属铂(II)配合物，化学式如通式(1)所示：
    Figure PCTCN2022088329-appb-100001
    其中，L为五元或六元杂芳环，
    R a和R b均不为氢原子且各自独立地代表烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合；
    R 1、R 2、R 3、R 4、R 5和R 6各自独立地代表氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合；
    R 1、R 2、R 3、R 4、R 5和R 6中的两个或者多个可以相连形成稠环，所述稠环还可以与其它环稠合；
    R u、R v、R w、R x和R y各自独立地表示单取代、双取代、三取代、四取代或者无取代，且R u、R v、R w、R x和R y各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合；且两个或者多个邻近的R u、R v、R w、R x和R y各自独立或者选择性连接形成稠环。
  2. 根据权利要求1所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料，其特征在于，具有如下化学结构，但是不仅限于此：
    Figure PCTCN2022088329-appb-100002
    Figure PCTCN2022088329-appb-100003
    Figure PCTCN2022088329-appb-100004
    Figure PCTCN2022088329-appb-100005
    Figure PCTCN2022088329-appb-100006
    Figure PCTCN2022088329-appb-100007
    Figure PCTCN2022088329-appb-100008
    Figure PCTCN2022088329-appb-100009
    Figure PCTCN2022088329-appb-100010
    Figure PCTCN2022088329-appb-100011
    Figure PCTCN2022088329-appb-100012
    Figure PCTCN2022088329-appb-100013
    Figure PCTCN2022088329-appb-100014
    Figure PCTCN2022088329-appb-100015
    Figure PCTCN2022088329-appb-100016
    Figure PCTCN2022088329-appb-100017
    Figure PCTCN2022088329-appb-100018
    Figure PCTCN2022088329-appb-100019
    Figure PCTCN2022088329-appb-100020
    Figure PCTCN2022088329-appb-100021
    Figure PCTCN2022088329-appb-100022
    Figure PCTCN2022088329-appb-100023
    其中，R均不为除甲基以外的烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基，或其氘代取代基。
  3. 一种权利要求1或2所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料在有机发光元件中的应用。
  4. 如权利要求3所述应用，其特征在于，所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池等。
  5. 一种如权利要求1或2所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料的应用，其特征在于，作为有机发光器件中的磷光发光材料或延迟荧光材料。
  6. 一种发光器件，其特征在于，包括第一电极、第二电极和有机层；有机层设置于第一电极和第二电极之间，且至少有一个有机层；所述有机层包括权利要求1或2所述发光材料。
  7. 根据权利要求6所述的发光器件，其特征在于，所述有机层为空穴注入层、空穴传输层、发光层或活性层、电子阻挡层或电子传输层中至少一层。
  8. 一种显示装置，其包括权利要求6所述的发光器件。
PCT/CN2022/088329 2021-04-22 2022-04-22 基于1,8-取代咔唑的高辐射速率铂配合物及应用 WO2022223011A1 (zh)

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