CN113621002B - Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof - Google Patents
Monocarborane-containing nitrogen heterocyclic carbene metal organic complex and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000010668 complexation reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003852 triazoles Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 13
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 9
- 150000003058 platinum compounds Chemical class 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims description 5
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 5
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- YWDVWNHKJKIBHC-UHFFFAOYSA-N methylideneplatinum Chemical compound [Pt]=C YWDVWNHKJKIBHC-UHFFFAOYSA-N 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a monocarborane-containing nitrogen heterocyclic carbene metal organic complex and a preparation method thereof, belonging to the technical field of organic synthesis, wherein the organic complex has the following structural general formula:wherein-CB 11 H 11 Is monocarborane(Is BH), -R 1 Represents C 4～12 N=1 to 3, x is a C element or an N element, and is a C element when a benzimidazole or imidazole ligand, and is an N element when a triazole. The carborane-containing nitrogen heterocyclic carbene platinum complex has the advantages of cheap and easily obtained raw materials, good economy, mild and easily controlled reaction conditions and higher yield; the compound has higher quantum yield and longer luminescence life; is favorable for industrial production and provides a novel economic and efficient method for preparing luminescent materials with good phosphorescence luminescent properties.
Description
[ field of technology ]
The invention belongs to the technical field of organic complex synthesis, and particularly relates to a monocarborane-containing nitrogen heterocyclic carbene metal organic complex and a preparation method thereof.
[ background Art ]
Organic light emitting diodes (oled) are novel optoelectronic devices that emit light autonomously, without a backlight source, with high luminous efficiency, high resolution, and lighter weight, which can effectively reduce the load of the light emitting device, expand the light emitting area, and have been widely used in mobile phones, computers, and outdoor large-sized displays. Organic light emitting diodes (oled) containing heavy metal coordination phosphorescent materials can enhance intersystem crossing (ISC) of electrons from a singlet state to a triplet state, greatly improve internal quantum efficiency, and are increasingly favored. Compared with the research on red and green electrophosphorescent materials, the research on blue phosphorescent luminescent materials is slow, the metal organic compounds suitable for serving as blue phosphorescent ligands are relatively less, and in addition, the lower luminous efficiency of the blue phosphorescent device is also an important problem.
[ invention ]
In order to solve the problems, the invention aims to provide a synthesis method of a phosphorescent light-emitting material with good economy, mild and easily controlled reaction conditions and high yield, in particular to a metal organic complex containing monocarborane nitrogen heterocyclic carbene and a preparation method thereof.
The invention is realized by the following technical scheme, and provides a monocarborane-containing nitrogen heterocyclic carbene metal organic complex which has the following structural general formula:
wherein, -CB 11 H 11 Is monocarborane(/>Is BH), -R 1 Represents C 4～12 N=1 to 3, x is a C element or an N element, and is a C element when a benzimidazole or imidazole ligand, and is an N element when a triazole.
The invention also provides a preparation method of the monocarborane-containing nitrogen heterocyclic carbene metal organic complex, which comprises the following steps:
s1 introducing the metal organic complex I into N 2 After 15min of bubbling, silver triflate was added to the mixture at N 2 Under the protection, adding a solvent for light-proof reaction for 1h, and heating a reaction container to enable the reaction temperature to reach 80 ℃ when precipitation is separated out;
s2, adding a carborane-containing ligand II, and carrying out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the N-heterocyclic carbene metal-organic complex containing monocarborane;
wherein, the structural formula of the metal organic complex I is as follows:
the structural formula of the carborane-containing ligand II is as follows:
in particular, the solvent is acetonitrile or tetrahydrofuran, the mol ratio of the metal organic complex I to the silver trifluoromethane sulfonate is 1: (2.5-3), and the metal organic complex I and the silver trifluoromethane sulfonate react in the dark in N 2 The reaction is carried out in an atmosphere without water and oxygen, the molar ratio of the metal organic complex I to the carborane-containing ligand II is 1:1.1-1.2, and the reflux reaction time is 6-8 h.
In particular, the preparation method of the compound I comprises the following steps:
s11, adding a platinum compound and a second solvent into the flask respectively;
s12 adding the compound III into a second solvent, after dissolving, dripping into a flask of S11, at 110 ℃ and N 2 And refluxing for 24 hours under protection, wherein the structural formula of the compound III is as follows:
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, separating and purifying by column chromatography to obtain the compound I.
Specifically, the molar ratio of the compound III to the platinum compound is 1: (1-1.2), the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
In particular, the preparation method of the carborane-containing ligand II comprises the following steps:
s21 carborane [ NMe ] 3 H][CB 11 H 12 ]Adding the mixture into a third solvent for dissolution;
s22 adding N-butyllithium under ice bath, and adding N 2 Adding cuprous iodide after reacting for 1.4-1.6h under protection, and reacting for 40min;
adding palladium catalyst, phosphine ligand and compound IV in ice bath, respectively, adding the catalyst into the solution, adding the phosphine ligand and the compound IV in the presence of N 2 Under the protection, reacting for 20-24 hours at room temperature, wherein the structural formula of the compound IV is as follows:R 2 is halo;
s24, filtering, washing and spin-drying the product obtained in the step S23, balancing with a counter cation reagent, and separating and purifying by column chromatography to obtain the carborane ligand II.
Specifically, the third solvent is dry tetrahydrofuran, the molar ratio of the compound IV to carborane is 1: (2-2.5), the molar ratio of carborane to n-butyllithium is 1: (1-1.3), and the molar ratio of carborane to cuprous iodide is 1: (1-1.3).
Specifically, the palladium catalyst is palladium acetate, and the molar ratio of the palladium catalyst to the cuprous iodide is 1:10.
In particular, the counter cation agent is tetraethylammonium bromide.
In particular, the phosphine ligand is tris (2-methoxyphenyl) phosphine, which has a molar ratio to cuprous iodide of 3:10.
The synthetic route of the invention is as follows:
the invention provides a monocarborane-containing nitrogen heterocyclic carbene metal organic complex and a preparation method thereof, and the monocarborane-containing nitrogen heterocyclic carbene metal organic complex has the following beneficial effects:
(1) The carborane-containing nitrogen heterocyclic carbene platinum complex has the advantages of cheap and easily obtained raw materials, good economy, mild and easily controlled reaction conditions and higher yield; the compound has higher quantum yield and longer luminescence life; is favorable for industrial production and provides a novel economic and efficient method for preparing luminescent materials with good phosphorescence luminescent properties.
(2) The raw materials are cheap and easy to obtain, the carborane-containing organometallic platinum (II) complex luminescent material is synthesized step by step, the quantum yield is higher, the luminescent life is longer, the manufacturing cost is lower, the method has good development prospect, the reaction conditions are easy to control, the method can be carried out under normal pressure and nitrogen atmosphere, the yield is higher, the operation is convenient, the method is suitable for industrial production, and the complex has potential application value in the fields of medicines, chemical industry, luminescent materials and the like.
[ description of the drawings ]
FIG. 1 is a metal-organic complex C according to example 1 of the present invention 1 A single crystal structure diagram of (2);
FIG. 2 is a metal-organic complex C according to example 2 of the present invention 2 Nuclear magnetic hydrogen spectrogram of (deuterated reagent is deuterated acetone);
FIG. 3 is a metal organic complex C according to example 2 of the present invention 2 Nuclear magnetic carbon spectrum (deuterated) the reagent is deuterated acetone);
FIG. 4 is a metal organic complex C according to example 2 of the present invention 2 [M+Na] + Is a high resolution mass spectrum of (2);
FIG. 5 shows a metal-organic complex C according to example 3 of the present invention 3 Nuclear magnetic hydrogen spectrogram of (deuterated reagent is deuterated acetone);
FIG. 6 is a metal-organic complex C according to example 3 of the present invention 3 Nuclear magnetic carbon spectrogram (deuterated reagent is deuterated acetone);
FIG. 7 is a metal organic complex C according to example 3 of the present invention 3 [M+Na]+high resolution mass spectrum.
FIG. 8 is a metal-organic complex C according to example 2 of the present invention 2 Ultraviolet-visible absorption spectrum in solution state;
FIG. 9 is a metal-organic complex C according to example 3 of the present invention 3 Ultraviolet-visible absorption spectrum in solution state;
FIG. 10 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in solid state;
FIG. 11 is a metal-organic complex C according to example 3 of the present invention 3 Emission spectrum in solid state;
FIG. 12 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in PMMA film state;
FIG. 13 is a metal-organic complex C according to example 3 of the present invention 3 Emission spectrum in PMMA film state;
FIG. 14 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in solution state;
FIG. 15 is a metal-organic complex C according to example 3 of the present invention 3 Emission profile in solution.
[ detailed description ] of the invention
The arrangement of the valence electron structure of the boron atom is 2s 2 2p 1 Due to its empty p π p π The orbitals are very strong electron-deficient atoms, have good charge transport properties, and are carborane anions [ CB ] 11 H 12 ] - There are 13 pairs of covalent electron delocalization in the whole ion and have three-dimensional aromaticity, and the delocalization of electrons makes the organic boride have special chemical stability and thermal stability. The formation of certain conjugated systems of carborane and halogenated bipyridyl can reduce the LUMO energy of the system, thereby changing the photophysical properties of the material. The strong electron donating property of the aza-carbene Pt (II) metal complex can reduce d-d transition of metal center, improve quantum yield, and the combination of the aza-carbene Pt (II) metal complex and a conjugated system of carborane can promote charge transmission and MLCT (metal-to-ligand charge transition), so that phosphorescence luminous efficiency is improved. The invention provides a monocarborane-containing azacyclo-carbene metal organic complex, which belongs to the technical field of organic synthesis and has the following structural general formula:
wherein, -CB 11 H 11 Is monocarborane(/>Is BH), -R 1 Represents C 4～12 N=1 to 3, x is a C element or an N element, and is a C element when a benzimidazole or imidazole ligand, and is an N element when a triazole.
The invention also provides a method for preparing the N-heterocyclic carbene metal-organic complex containing monocarborane, which comprises the following steps:
s1 introducing the metal organic complex I into N 2 After 15min of bubbling, silver triflate was added to the mixture at N 2 Under the protection, adding a solvent for light-proof reaction for 1h, and heating a reaction container to enable the reaction temperature to reach 80 ℃ when precipitation is separated out;
s2, adding a carborane-containing ligand II, and carrying out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the N-heterocyclic carbene metal-organic complex containing monocarborane;
wherein, the structural formula of the metal organic complex I is as follows:
the structural formula of the carborane-containing ligand II is as follows:
in the invention, the solvent is acetonitrile or tetrahydrofuran, the mol ratio of the metal organic complex I to the silver trifluoromethane sulfonate is 1: (2.5-3), and the metal organic complex I and the silver trifluoromethane sulfonate react in the dark under N 2 Atmosphere anhydrousThe reaction is carried out under oxygen, the molar ratio of the metal organic complex I to the carborane-containing ligand II is 1: (1.1-1.2), and the reflux reaction time is 6-8 h, preferably 8h.
In the invention, the preparation method of the compound I and the complex VII comprises the following steps:
s11, adding a platinum compound and a second solvent into the flask respectively;
s12 adding the compound III into a second solvent, after dissolving, dripping into a flask of S11, at 110 ℃ and N 2 And refluxing for 24 hours under protection, wherein the structural formula of the compound III is as follows:
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, separating and purifying by column chromatography to obtain the compound I.
In particular, the molar ratio of the compound III to the platinum compound is 1: (1 to 1.2), preferably 1: (1.1), optimally 1:1, wherein the platinum compound is platinum acetylacetonate and the second solvent is dimethyl sulfoxide.
In the invention, the preparation method of the carborane-containing ligand II comprises the following steps:
s21 carborane [ NMe ] 3 H][CB 11 H 12 ]Adding the mixture into a third solvent for dissolution;
s22 adding N-butyllithium under ice bath, and adding N 2 Adding cuprous iodide after reacting for 1.4-1.6h under protection, and reacting for 40min;
adding palladium catalyst, phosphine ligand and compound IV in ice bath, respectively, adding the catalyst into the solution, adding the phosphine ligand and the compound IV in the presence of N 2 Under the protection, reacting for 20-24 hours at room temperature, wherein the structural formula of the compound IV is as follows:R 2 is halo;
s24, filtering, washing and spin-drying the product obtained in the step S23, balancing with a counter cation reagent, and separating and purifying by column chromatography, wherein the counter cation reagent is tetraethylammonium bromide.
The carborane-containing ligand II needs to be in N in the preparation process 2 The reaction is carried out under protection, the temperature of the reaction is room temperature, but the reaction bottle is subjected to ice bath for 5min in advance before each feeding.
In particular, the third solvent is dry tetrahydrofuran, and the molar ratio of the compound IV to carborane is 1: (2-2.5), preferably 1:2.2; the molar ratio of carborane to n-butyllithium is 1: (1-1.3), preferably 1:1.2, the molar ratio to cuprous iodide is 1: (1 to 1.3), preferably 1:1.1.
specifically, the palladium catalyst is palladium acetate, and the molar ratio of the palladium catalyst to the cuprous iodide is 1:10.
In particular, the phosphine ligand is tris (2-methoxyphenyl) phosphine, which has a molar ratio to cuprous iodide of 3:10.
The synthetic route for preparing carborane-containing azacyclo-carbene metal organo-platinum complexes from compounds I and II is as follows:
in order that the invention may be more readily understood, a further explanation of the invention in connection with specific embodiments is provided below, and descriptions of well-known functions and constructions are omitted for clarity and conciseness.
Example 1
This example provides a metal-organic platinum complex C 1 The structural formula is as follows:
metal organic platinum complexes C 1 The synthetic route of (2) is as follows:
metal organic platinum complexes C 1 The preparation method comprises the following specific steps:
(i) Platinum acetylacetonate (4.89 mmol,1.9 g) was added to a 250mL two-necked round bottom flask followed by 4mL dimethyl sulfoxide; by reacting compound III 1 (4.44 mmol,2 g) was dissolved in a 50mL beaker containing 20mL dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, the constant pressure dropping funnel was inserted into a side port of the flask, and the opening of a piston was controlled so that the solution was dropped dropwise into the flask over 3 hours to allow the two to react sufficiently. Reflux is carried out for 24h under the protection of nitrogen at 110 ℃. After the reaction was completed, the solvent was distilled off under reduced pressure, 50mL of methylene chloride was added to the residue, and the residue was washed twice with 50mL of water; anhydrous MgSO for organic phase 4 Drying, filtering, concentrating under reduced pressure, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate=4/1) to obtain white solid I 1 2.11g, 73.8% yield.
(ii) Carborane [ NMe ] 3 H][CB 11 H 12 ](2.96 mmol,600 mg) was dissolved in 20ml of tetrahydrofuran under nitrogen atmosphere, stirred, 6ml of n-butyllithium was added under ice bath, after stirring for 1.5 hours, cuprous iodide (3.25 mmol,620 mg) was added under ice bath, after 40 minutes of reaction, palladium acetate (0.33 mmol,73 mg), tris (2-methoxyphenyl) phosphine (0.99 mmol,349 mg), and Compound IV were added under ice bath 1 (1.33 mmol,417 mg) was stirred under nitrogen for 12h. After the reaction is finished, filtering by diatomite, washing with dichloromethane for multiple times, spin-drying filtrate, adding 50ml of methyl tertiary butyl ether for extraction, washing with 20ml of 1mol/L hydrochloric acid, taking an ether layer, adding 20ml of water, spin-drying the ether layer, adding a proper amount of sodium hydroxide solution into the water for neutralizing until the water solution is alkaline, adding tetraethylammonium bromide to form off-white gray precipitate, filtering, separating and purifying by column chromatography (eluent: ethyl acetate/methanol=100/1) to obtain a white solid II 1 0.612g, 65.3% yield.
(iii) By reacting compound I 1 (0.23 mmol,150 mg) and silver trifluoromethane sulfonate (0.58 mmol,148 mg) were added to a sealed, light-tight, 100ml, eggplant-shaped bottle, which was then repeatedly evacuated and purged with nitrogen. 20ml of degassed tetrahydrofuran was added to the reaction flask, followed byReflux is carried out for 1h under the protection of nitrogen at 80 ℃; after precipitation, the compound II 1 (0.25 mmol,177 mg) was quickly placed in a reaction flask, and the reaction was continued for 8 hours. After the reaction, filtering, decompressing and removing the solvent, separating and purifying by column chromatography (eluent: dichloromethane) to obtain white solid C 1 0.156g, 73.5% yield.
Example 2
This example provides a metal organic complex C 2 The structural formula is as follows:
metal organic complexes C 2 The synthetic route of (2) is as follows:
metal organic complexes C 2 The preparation method comprises the following specific steps:
(i) Platinum acetylacetonate (2.80 mmol,1.1 g) was added to a 250mL two-necked round bottom flask followed by 4mL dimethyl sulfoxide; by reacting compound III 2 (2.58 mmol,2 g) was dissolved in a 50mL beaker containing 20mL dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, the constant pressure dropping funnel was inserted into a side port of the flask, and the opening of a piston was controlled so that the solution was dropped dropwise into the flask over 3 hours to allow the two to react sufficiently. Reflux is carried out for 24h under the protection of nitrogen at 110 ℃. After the reaction was completed, the solvent was distilled off under reduced pressure, 50mL of methylene chloride was added to the residue, and the residue was washed twice with 50mL of water; anhydrous MgSO for organic phase 4 Drying, filtering, concentrating under reduced pressure, and purifying by column chromatography (eluent: dichloromethane) to obtain white solid I 2 1.88g, 75.0% yield.
(ii) Carborane [ NMe ] 3 H][CB 11 H 12 ](2.96 mmol,600 mg) was dissolved in 20ml of tetrahydrofuran under nitrogen atmosphere, stirred, 6ml of n-butyllithium was added under ice bath, and the reaction was stirred for 1.5 hoursCuprous iodide (3.25 mmol,620 mg) was added to the ice bath, and after 40min of reaction, palladium acetate (0.33 mmol,73 mg), tris (2-methoxyphenyl) phosphine (0.99 mmol,349 mg) and Compound IV were added to the ice bath 2 (1.33 mmol,417 mg) was stirred under nitrogen for 12h. After the reaction is finished, filtering by diatomite, washing with dichloromethane for multiple times, spin-drying filtrate, adding 50ml of methyl tertiary butyl ether for extraction, washing with 20ml of 1mol/L hydrochloric acid, taking an ether layer, adding 20ml of water, spin-drying the ether layer, adding a proper amount of sodium hydroxide solution into the water for neutralizing until the water solution is alkaline, adding tetraethylammonium bromide to form off-white gray precipitate, filtering, separating and purifying by column chromatography (eluent: ethyl acetate/methanol=100/1) to obtain a white solid II 2 0.581g, yield 62.0%.
(iii) By reacting compound I 2 (0.13 mmol,126 mg) and silver trifluoromethane sulfonate (0.32 mmol,83 mg) were added to a 100ml branched eggplant-shaped bottle sealed from light, and then repeatedly evacuated and purged with nitrogen. Adding 20ml of degassed tetrahydrofuran into a reaction bottle, and refluxing for 1h under the protection of nitrogen at 80 ℃; after precipitation, the compound II 2 (0.143 mmol,100 mg) was rapidly introduced into the reaction flask and the reaction was continued for 8 hours. After the reaction, the mixture was filtered and the solvent was removed under reduced pressure, followed by separation and purification by column chromatography (eluent: dichloromethane/n-hexane=3/1) to give a white solid C 2 0.102 g, yield 63.0%.
Example 3
This example provides a metal organic complex C 3 The structural formula is as follows:
metal organic complexes C 3 The synthetic route of (2) is as follows:
metal organic complexes C 3 The preparation method comprises the following specific steps:
(i) Platinum acetylacetonate (3.26 mmol,1.3 g) was added to a 250mL two-necked round bottom flask followed by 4mL dimethyl sulfoxide; by reacting compound III 3 2.96mmol,2 g) was dissolved in a 50mL beaker containing 20mL dimethyl sulfoxide, the beaker was slightly heated to promote dissolution, and then transferred to a 60mL constant pressure dropping funnel, the constant pressure dropping funnel was inserted into a side port of the flask, and the opening of a piston was controlled so that the solution was dropped into the flask dropwise over 3 hours to allow the two to react sufficiently. Reflux is carried out for 24h under the protection of nitrogen at 110 ℃. After the reaction was completed, the solvent was distilled off under reduced pressure, 50mL of methylene chloride was added to the residue, and the residue was washed twice with 50mL of water; anhydrous MgSO for organic phase 4 Drying, filtering, concentrating under reduced pressure, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate=4/1) to obtain white solid I 3 1.85g, yield 72.0%.
(ii) For specific steps reference is made to example 1 (ii).
(iii) By reacting compound I 3 (0.13 mmol,113 mg) and silver trifluoromethane sulfonate (0.32 mmol,83 mg) were added to a 100ml bottle with a eggplant shape, which was sealed and protected from light, and then the vacuum was repeatedly pulled, and nitrogen gas was introduced. Adding 20ml of degassed tetrahydrofuran into a reaction bottle, and refluxing for 1h under the protection of nitrogen at 80 ℃; after precipitation, the compound II 1 (0.143 mmol,100 mg) was rapidly introduced into the reaction flask and the reaction was continued for 8 hours. After the reaction, filtering, decompressing and removing the solvent, separating and purifying by column chromatography (eluent: dichloromethane) to obtain white solid C 3 0.112g, 75.5% yield.
In order to verify the feasibility of the metal-organic complexes prepared by the process described in the present application, the following explanation is made experimentally.
Experimental example 1
The metal organic complex C synthesized by the invention 1 、C 2 、C 3 The structural characterization data of (2) are as follows:
FIG. 1 is a metal-organic complex C according to example 1 of the present invention 1 FIG. 2 is a single crystal structure of a metal-organic complex C according to example 2 of the present invention 2 Is shown in FIG. 3 (deuterated reagent is deuterated acetone) and its nuclear magnetic carbon spectrum (deuterated reagent is deuterated acetone)) FIG. 4 is a high resolution spectrum of the metal-organic complex C of example 3 of the present invention of FIG. 5 3 The nuclear magnetic hydrogen spectrogram of (a deuterated reagent is deuterated acetone), the nuclear magnetic carbon spectrogram of (a deuterated reagent is deuterated acetone) is shown in fig. 6, and the high-resolution mass spectrogram of (a deuterated reagent is deuterated acetone) is shown in fig. 7.
Experimental example 2
FIGS. 8 and 9 are, respectively, metal-organic complexes C prepared according to the invention 2 And metal organic complexes C 3 In the state of solution (metal-organic complex C 2 And metal organic complexes C 3 Respectively dissolved in methylene chloride) at 25 ℃.
Experimental example 3
FIGS. 10 and 11 are respectively a metal-organic complex C prepared according to the present invention 2 And metal organic complexes C 3 Phosphorescent emission spectra at 25 ℃ in solid state, excitation wavelengths were 356nm and 328nm, respectively. FIGS. 12 and 13 are respectively a metal-organic complex C prepared according to the present invention 2 And metal organic complexes C 3 Phosphorescent emission spectra at 25 ℃ in PMMA film state have excitation wavelengths of 356nm and 328nm respectively. Wherein, the addition amount of the metal organic complex in the PMMA film is 2wt percent, and the rest is PMMA (PMMA film is prepared by adopting a conventional method, for example, a metal organic complex sample and polymethyl methacrylate are dissolved in methylene dichloride (ACS grade) according to the mass ratio of 1:49, and the solution is dripped on the surface of quartz glass, and the solvent is volatilized.
FIGS. 14 and 15 are respectively a metal-organic complex C prepared according to the present invention 2 And metal organic complexes C 3 In the state of solution (metal-organic complex C 2 And metal organic complexes C 3 Respectively dissolved in methylene chloride) at 25 deg.c, excitation wavelengths of 356nm and 328nm, respectively.
The emission maps of fig. 10 to 15 are normalized results, so that comparison is convenient. The specific normalization method is a conventional normalization method, such as: the spectral data is divided by the highest peak at the same time, so that the highest peak becomes 1.
The metal organic complex C prepared by the invention is as follows 2 Sum goldBelonging to organic complex C 3 The luminescence properties under the different conditions are summarized, and are specifically shown in table 1, and table 1 shows the luminescence properties of different metal-organic complexes under different conditions.
TABLE 1
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Claims (10)
1. The N-heterocyclic carbene metal-organic complex containing monocarborane is characterized by having the following structural general formula:
wherein, -CB 11 H 11 Is monocarborane Is BH, -R 1 Represents C 4～12 N=1 to 3, x is a C element or an N element, and is a C element when a benzimidazole or imidazole ligand, and is an N element when a triazole.
2. A process for the preparation of a monocarborane-containing azacyclo-carbene metal organic complex according to claim 1, comprising the steps of:
s1 introducing the metal organic complex I into N 2 After 15min of bubbling, silver triflate was added to the mixture at N 2 Under the protection, adding solvent to react for 1h in a dark place, and heating a reaction container to make the reaction temperature to be high when precipitation is separated outThe degree reaches 80 ℃;
s2, adding a carborane-containing ligand II, and carrying out reflux reaction under the same condition;
s3, filtering, decompressing, removing the solvent, and separating and purifying by column chromatography to obtain the N-heterocyclic carbene metal-organic complex containing monocarborane;
wherein, the structural formula of the metal organic complex I is as follows:
the structural formula of the carborane-containing ligand II is as follows:
3. the method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 2, wherein the solvent is acetonitrile or tetrahydrofuran, the molar ratio of the metal organic complex I to the silver trifluoromethane sulfonate is 1: (2.5-3), so that bromine in the complex I is completely precipitated in the form of silver bromide, and the next coordination reaction with the ligand II can be completely carried out, wherein the metal organic complex I and the silver trifluoromethane sulfonate react in the dark in N 2 The reaction is carried out in an atmosphere without water and oxygen, the molar ratio of the metal organic complex I to the carborane-containing ligand II is 1:1.1-1.2, and the reflux reaction time is 6-8 h.
4. The method for preparing the monocarborane-containing azacyclo-carbene metal organic complex according to claim 2, wherein the method for preparing the metal organic complex I is as follows:
s11, adding a platinum compound and a second solvent into the flask respectively;
s12 adding the compound III into a second solvent, after dissolving, dripping into a flask of S11 at 110 ℃, andN 2 and refluxing for 24 hours under protection, wherein the structural formula of the compound III is as follows:
s13, decompressing, removing the second solvent, adding dichloromethane, washing, drying, filtering, decompressing, separating and purifying by column chromatography to obtain the compound I.
5. The method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 4, wherein the molar ratio of the compound III to the platinum compound is 1: (1-1.2), the platinum compound is platinum acetylacetonate, and the second solvent is dimethyl sulfoxide.
6. The method for preparing the monocarborane-containing nitrogen heterocyclic carbene metal organic complex according to claim 2, wherein the method for preparing the carborane-containing ligand II is as follows:
s21 carborane [ NMe ] 3 H][CB 11 H 12 ]Adding the mixture into a third solvent for dissolution;
s22 adding N-butyllithium under ice bath, and adding N 2 Adding cuprous iodide after reacting for 1.4-1.6h under protection, and reacting for 40min;
adding palladium catalyst, phosphine ligand and compound IV in ice bath, adding the catalyst into the solution, adding the phosphine ligand and compound IV in the presence of N 2 Under the protection, reacting for 20-24 hours at room temperature, wherein the structural formula of the compound IV is as follows:R 2 is halo;
s24, filtering, washing and spin-drying the product obtained in the step S23, balancing with a counter cation reagent, and separating and purifying by column chromatography to obtain the carborane ligand II.
7. The method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 6, wherein the third solvent is dry tetrahydrofuran, the molar ratio of the compound IV to carborane is 1: (2-2.5), the molar ratio of carborane to n-butyllithium is 1: (1-1.3), and the molar ratio of carborane to cuprous iodide is 1: (1-1.3).
8. The method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 6, wherein the palladium catalyst is palladium acetate and the molar ratio of palladium acetate to cuprous iodide is 1:10.
9. The method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 6, wherein the counter cation reagent is tetraethylammonium bromide.
10. The method for preparing a monocarborane-containing azacyclo-carbene metal organic complex according to claim 6, wherein the phosphine ligand is tris (2-methoxyphenyl) phosphine, and the molar ratio of phosphine ligand to cuprous iodide is 3:10.
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