CN102219797B - N-heterocyclic carbene annular metal complexes, preparation method and purpose thereof - Google Patents
N-heterocyclic carbene annular metal complexes, preparation method and purpose thereof Download PDFInfo
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- CN102219797B CN102219797B CN201110102622.1A CN201110102622A CN102219797B CN 102219797 B CN102219797 B CN 102219797B CN 201110102622 A CN201110102622 A CN 201110102622A CN 102219797 B CN102219797 B CN 102219797B
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- carbene
- heterocyclic carbene
- metal complex
- cyclic
- silver
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 title claims abstract description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- -1 N-heterocyclic carbene cyclic metal complex Chemical class 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 abstract description 3
- 239000007850 fluorescent dye Substances 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 15
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 13
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SHPPDRZENGVOOR-UHFFFAOYSA-N 1-butylbenzimidazole Chemical compound C1=CC=C2N(CCCC)C=NC2=C1 SHPPDRZENGVOOR-UHFFFAOYSA-N 0.000 description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- QQTZYHKWYUCCFC-UHFFFAOYSA-N 1-(pyridin-2-ylmethyl)benzimidazole Chemical compound C1=NC2=CC=CC=C2N1CC1=CC=CC=N1 QQTZYHKWYUCCFC-UHFFFAOYSA-N 0.000 description 1
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- QHCCOYAKYCWDOJ-UHFFFAOYSA-N 2-ethyl-1h-benzimidazole Chemical compound C1=CC=C2NC(CC)=NC2=C1 QHCCOYAKYCWDOJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- YCTWFEPMSJMWAJ-UHFFFAOYSA-N [Ag].C1=CC=CC2=CC=CC=C12 Chemical compound [Ag].C1=CC=CC2=CC=CC=C12 YCTWFEPMSJMWAJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical compound CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical group C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention discloses N-heterocyclic carbene annular metal complexes with 1,5-di[1-substituent-3 imidazole ethyl] naphthol diether and 1,4-di[1-substituent-3 benzimidazole ethyl]diphenyl ether as precursors and the preparation method thereof. R in the N-heterocyclic carbene is independent or is combined with other elements to form hydrogen or C1_C6 organic radical, wherein the C1_C6 organic radical contains one or more selected from the group consisting of alkyl group, branched alkyl group, naphthenic base, cycloalkenyl group, alkynyl, aryl group, arylalkyl, heterocycle, alkoxy and substitution derivatives of alkoxy. The N-heterocyclic carbene annular metal complexes provided by the invention are mainly applied in the technical field of fluorescent agents.
Description
Statement regarding sponsoring research or development
The invention is based on the national natural science fund (the fund number is
20872111
) And Tianjin City Natural science fund (fund number is
11JCZDJC22000
) Under the subsidization of (1).
Technical Field
The invention belongs to the technical field of organic synthesis and metal organic chemistry, and relates to synthesis of a nitrogen heterocyclic carbene cyclic metal complex, in particular to a nitrogen heterocyclic carbene cyclic metal complex
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
A preparation method and application of an N-heterocyclic carbene cyclic metal complex taking phenylether as a precursor.
Background
Metal organic chemistry is one of the key topics of research in the chemical field at present, and not only brings the progress of a novel synthesis method, but also brings the update and development of a new material. Metal carbene complexes are one of the leading fields of research in metal organic chemistry. In that
1991
Year of year
Arduengo
The first separation gives a stable free form
N-
Heterocyclic carbenes
(NHC)
After that time, the user can use the device,
N-
the study of heterocyclic carbene metal complexes has progressed rapidly over the last two decades.
N-
The heterocyclic carbenes have a higher bond energy for coordination to the metal than the corresponding organophosphines, and they are more compatible than the organophosphine complexesThe advantages shown are mainly due to their higher stability to high temperatures, humidity and oxidizing agents. From the point of view of its field of application,
N-
the heterocyclic carbene metal complex is a novel catalyst with high activity and high selectivity, and has good application prospect in homogeneous catalytic reaction. In addition to this, the present invention is,
N-
the heterocyclic carbene metal complex can also be applied to the fields of material science, photochemistry and the like. Fluorescent molecular switches comprising metal-ion complexes have received great interest from scientists in recent years because metal-ion complexes can be used both as fluorophores with delayed emission
,
Can also be used as receptor, and can play dual roles simultaneously. Fluorescent molecular switches are mostly structures of the "fluorophore-stroma-receptor" type, or a combination of several such identical moieties or different moieties. The metal complex has unique characteristics as a component of a fluorescent molecular switch, namely has the characteristics of high sensitivity, simplicity, reliability and the like. With the further research and the expansion of the research scope,
N-
the heterocyclic carbene metal complex is used as a subject compound of a fluorescence switch and is applied to the fields of chemical disciplines, life disciplines, environmental analysis, clinical medicine and the like.
Disclosure of Invention
The object of the present invention is to provide
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
N-heterocyclic carbene cyclic metal complexes as precursors of phenylenediethers, in particular by
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethersAnd
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
A cyclic complex of azacyclo-carbene silver with a phenylether as precursor.
The invention also relates to the N-heterocyclic carbene silver cyclic complex and a preparation method thereof.
The invention relates to the calibration of the hydrogen spectrum of the metal organic compound.
The invention relates to a method for growing crystals of the metal organic matters, measurement data and research of the data.
The metal organic cyclic complex is obtained by culturing through a diffusion or volatilization method.
The metal organic cyclic complex is subjected to nuclear magnetic data characterization and fluorescence data determination.
The invention further provides a method for preparing the N-heterocyclic carbene cyclic metal complex under the protection of inert gas, and the method is subjected to crystallography characterization.
The metal organic complexes of the invention are prepared by
X-
And (4) carrying out determination and data characterization by using a ray diffractometer.
The invention further relates to a method for preparing the same
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
N-heterocyclic carbene cyclic metals as precursors to phenylenediethersThe complex is mainly applied to the technical field of fluorescent agents.
In order to accomplish the above objects, the technical solution of the present invention is as follows:
with the passage of
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers (C)
1
) And
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
Benzenediether (b)
2
) An azacyclo-carbene cyclic metal complex as a precursor (
I
) And (a)
II
）：
（1）
（2）
（I）
（II）
Wherein,
R
are independently or in combination hydrogen or
1C
—
6C
An organic group, a hydroxyl group, a carboxyl group,
1C
—
6C
the organic group includes an alkyl group, a branched alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an arylalkyl group, a nitrogen-containing heterocycle, or an alkoxy group.
Is a metal cation of silver or palladium,
m
is composed of
1-4
；
-X
Halogen anions or hexafluorophosphate anions.
Wherein,
1C
—
6 C
the organic radicals being selected from alkyl radicals, e.g.
2 5CH
、
6 13CH
(ii) a Branched alkyl groups such as isobutyl, n-butyl or neopentyl; cycloalkyl groups such as cyclopropanemethyl or cyclobutaneethyl; alkenyl groups such as vinyl, propenyl, or allyl; cycloalkenyl such as cyclopropenyl; alkynyl groups such as ethynyl; aryl groups such as benzyl, naphthylmethyl, anthracenemethyl; nitrogen-containing heterocycles and substituted derivatives thereof, e.g. ethylimidazole, n-butylimidazole, benzylimidazole, ethylbenzimidazole, n-butylbenzimidazole or
1-
Picolylbenzimidazole.
The halogen is selected from chlorine, bromine and iodine, preferably iodide.
The invention discloses a preparation method of an N-heterocyclic carbene cyclic metal complex, which is characterized by comprising the following steps:
under the protection of inert gas, will pass
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The N-heterocyclic carbene salt and the metal compound which take the benzene diether as the precursor have the molar ratio of
0.5-3
～
2-6
Is added into a reaction vessel in proportion, dissolved by a water-removed high-purity organic solvent, and then
0
℃～
100
Reaction at a temperature of DEG C
12
～
24
And (4) filtering and naturally volatilizing the solution to obtain the carbene cyclic metal complex.
The metal compound is selected from one of silver oxide, silver acetate, silver carbonate, anhydrous mercury acetate, mercury halide, cuprous iodide, cuprous oxide, lithium carbonate, nickel acetate, palladium chloride and acetonitrile palladium chloride. Preferably silver acetate, silver carbonate, mercury halide, cuprous oxide, nickel acetate, palladium acetate, zirconium oxide, palladium chloride or acetonitrile palladium chloride. More preferably silver oxide, anhydrous mercuric acetate or acetonitrile palladium chloride.
The organic solvent is selected from tetrahydrofuran (tetrahydrofuran)
THF
) Dichloromethane, trichloromethane,
1
，
2-
Dichloroethane, acetone, diethyl ether, acetonitrile, nitroethane,
N
，
N-
Any one of dimethylformamide, dimethyl sulfoxide or a mixture thereof. Preferably acetone,
1
，
2-
Dichloroethane, ethylene dichloride,
N
，
N-
Dimethylformamide or dimethyl sulfoxide, more preferably tetrahydrofuran(s) ((R))
THF
) Dichloromethane or acetonitrile. Wherein the mixed solvent is
THF
And dichloromethane.
The nitrogen heterocyclic carbene cyclic metal complex provided by the invention has the following typical metal complexes:
the invention discloses a method for preparing
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The application of the N-heterocyclic carbene cyclic metal complex taking the benzene diether as a precursor in the aspect of being used as a fluorescent agent.
The molecular formula of the typical N-heterocyclic carbene silver cyclic complex is
48 56 2 12 8 4 2CHAgFNOP
。
The molecular formula of another N-heterocyclic carbene silver ring complex is
64 76 2 12 8 4 2CHAgFNOP
Is particularly described by
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The data of the single crystal of the nitrogen heterocyclic carbene silver cyclic complex taking the phenylether as the precursor are as follows:
crystal data and structure refinement parameters are included in the supporting information. In that
Bruker SMART 1000 CCD
On a diffractometer, the experimental temperature is
113(2)K,
In that
50kV
And
20mA
by using
Mo-Ka
Radiation of radiation
(0.71073Å)
Operation with
SMART
And
SAINT
the software performs the collection and restoration of the data,
q
in the range of
1.8 < q < 25
And (5) performing annealing. Applications of
SADABS
The program performs an empirical absorption correction. The crystal structure being solved by direct methods using
SHELXTL
And performing full matrix least square correction on all non-hydrogen atom coordinate anisotropic thermal parameters.
The N-heterocyclic carbene metal complex disclosed by the invention is in a parallel relationship and has no priority major and minor.
The invention further discloses a method for preparing the same
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The N-heterocyclic carbene cyclic metal complex taking the phenylether as the precursor is mainly applied to the technical field of fluorescent agents.
Experiments prove that: by passing
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The fluorescence emission intensity of the N-heterocyclic carbene cyclic metal complex taking the phenylether as the precursor is stronger than that of the corresponding ligand, and the fluorescence change is obvious. In that
298K
Acetonitrile (a)
1
×
10
－
5
mol/L
) Excitation wavelength in solution of
232nm
Under the condition, the fluorescence quenching pattern of the p-phenylenediamine for molecular recognition is shown in the attached drawing of the specification
3
And
4
。
the invention proposes to pass
1,5-
II
[1-
Substituent group
-3
Imidazole ethyl radical
]
Naphthalene diethers and
1,4-
II
[1-
Substituent group
-3
Benzimidazole ethyl radical
]
The N-heterocyclic carbene cyclic metal complex with the phenylether as the precursor is a high-grade fluorescent material which can stably exist in a standard state, has the advantages of adjustable structure, simple preparation and obvious fluorescent photosensitive effect, can be used for preparing fluorescent materials and fluorescent molecule recognition systems, and is expected to be applied in the field of fluorescent chemistry.
Description of the drawings:
drawing (A)
1
Being silver-containing complexes (examples)
3
) The crystal structure of (1);
drawing (A)
2
Being silver-containing complexes (examples)
4
) The crystal structure of (1);
drawing (A)
3
Being silver-containing complexes (examples)
3
) In a crystal of
298K
Acetonitrile (a)
1
×
10
－
5
mol/L
) Excitation wavelength in solution of
232nm
Under the condition, a fluorescence quenching graph;
drawing (A)
4
Being silver-containing complexes (examples)
4
) In a crystal of
298K
Acetonitrile (a)
1
×
10
－
5
mol/L
) Excitation wavelength in solution of
232nm
Under the condition, fluorescence quenching pattern.
Detailed Description
For the purposes of simplicity and clarity, descriptions of well-known technologies are omitted appropriately below so as not to obscure the description of the present technical solution with unnecessary details. The invention is further described in conjunction with the preferred embodimentsIn particular, the starting materials for preparing the compounds of the invention are described
1,5-
The dihydroxy naphthalene is a mixture of a dihydroxy naphthalene,
1,4-
the reaction product of a dihydroxy benzene and a dihydroxy benzene,
1,2-
the dibromoethane is used for the reaction of ethylene,
1-
the ethyl imidazole is used for preparing the water-soluble polymer,
1-
n-butylbenzimidazole and the like are commercially available or can be easily prepared by known methods.
The reagents used for preparing the compound are all from Yueli and Kowii chemical Co., Ltd, Tianjin, and the grade is analytical purity.
It should be further noted that: all experimental procedures were performed
Schlenk
Technically, the solvent is purified by a standard procedure. All reagents used for synthesis and analysis were analytically pure and were not further processed. Melting point through
Boetius
And (5) measuring by using a zone cutter.
1
H NMR
Spectral passing mercury variable
Vx400
Spectrophotometer recording, measurement interval:
400 MHz
. Chemical shifts, delta, according to international standards
TMS
And (4) measuring. Fluorescence spectrum through
Cary Eclipse
And (4) measuring by a fluorescence spectrometer.
Examples
1
Will be provided with
NaOH (2.997 g, 74.9 mmol)
Are prepared into
30 mL
To which tetrabutylammonium bromide was added as an aqueous solution
(0.201g, 0.6 mmol)
Will be
1,5-
Dihydroxynaphthalene
(2.000 g, 12.5 mmol)
Dissolved in
40 mL1,2-
Dibromo ethyl esterMixing the two solutions, and heating to
80 ˚C
Stirring the mixture
12h
. Separating the brown organic layer by separating the aqueous layer, and evaporating the organic layer by a rotary evaporator
1,2-
The dibromoethane is separated out and added into the residual substance
80ml
Then with water of
3CHCl
Extraction of
3
Then, use each time
30ml
Then, the extracted solution was dried over anhydrous magnesium sulfate. Thereafter separating the chloroform to obtain
1,5-
II
[2
’
-
Bromoethyl radical
]
Light brown powder of naphthalene diether. Yield:
2.737 g (59%)
. Melting point:
140-142 ˚C
。
1
Z, 6H NMR (400 MHDMSO-d):
δ
J H 2 J H 2 J H J H J H 3.95 (t, = 6.5, 4H, C), 4.49 (t, = 6.5, 4H, C), 7.03 (d, = 3.8, 2H, Ph), 7.43 (d, = 3.8, 2H, Ph), 7.80 (d, = 3.8, 2H, Ph)
。
II
[2
’
-
Bromoethyl radical
]
Naphthalene diethers
(4.000 g, 10.7 mmol)
And
1-
ethylimidazole
(2.468 g, 25.7 mmol)
In tetrahydrofuran solution of
(150 mL)
Stirring for seven days to precipitate a pale yellow solid, filtering, washing with tetrahydrofuran to obtain a yellow solid
1,5-
II
[1-
Ethyl radical
-3
Imidazole ethyl radical
]
Naphthalene diether bromide. Yield of：
4.542 g (75%)
. Melting point:
166-168 ˚C
。
adding into methanol solution
1,5-
II
[1-
Ethyl radical
-3
Imidazole ethyl radical
]
Naphthalene diether bromide
(2.000 g, 3.5 mmol)
Added with stirring at room temperature
4 6NHPF (1.382 g, 8.5 mmol)
Stirring to separate out yellow precipitate. Filtering, washing the solid with methanol to obtain the ligand
1,5-
II
[1-
Ethyl radical
-3
Imidazole ethyl radical
]
Naphthalene diether hexafluorophosphate. Yield:
1.810 g (81%)
. Melting point:
200-202 ˚C
。
1
Z, 6H NMR (400 MHDMSO-d):
δ
J H 3 J H 2 J H 2 J H 2 J H J H J H H H H 1.42 (t, = 7.2, 6H, C), 4.25 (q, = 7.2, 4H, C), 4.47 (t, = 4.4, 4H, C), 4.75 (t, = 4.4, 4H, C), 7.04 (d, = 8.0, 2H, Ph), 7.35 (t, = 8.0, 2H, Ph), 7.64 (d, = 8.0, 2H, Ph), 7.83 (s, 2H, 4 or 5-imi), 7.95 (s, 2H, 4 or 5-imi), 9.38 (s, 2H, 2-imi) (imi = imidazole)
。
the experimental flow is shown in the following chart:
examples
2
1,4-
II
[2
’
-
Bromoethyl radical
]
Preparation and preparation of benzenediethers
1,5-
II
[2
’
-
Bromoethyl radical
]
Naphthalene diether analogs
,
Only will
1,5-
Conversion of dihydroxynaphthalene to
1,4-
Dihydroxybenzene. Yield:
3.216 g (55%)
melting point:
102-104 ˚C
。
1
Z, 3H NMR (400 MHCDCl):
δ
J H 2 J H 2 H3.60 (t, = 6.0, 4H, C), 4.24 (t, = 6.0, 4H, C), 6.86 (s, 4H, Ph)
。
II
[1-
N-butyl
-3
Benzimidazole ethyl radical
]
Preparation and preparation of benzenediether hexafluorophosphate
2
Similarity of
,
Only that
1,5-
II
[2
’
-
Bromoethyl radical
]
Naphthalene diethers and
1-
conversion of ethylimidazole to
1,4-
II
[2
’
-
Bromoethyl radical
]
Benzenediether and
1-
n-butylbenzimidazole, the product obtained being reacted with
4 6NHPF
And carrying out exchange. Yield:
1.960 g (82%)
melting point:
218-220 ˚C
。
1
Z 6H NMR (400 MH, DMSO-d):
δ
J H 3 H 2 H 2 J H 2 J H J H 2 H H H 1.73 (t, = 5.4, 6H, C), 2.15 (m, 4H, C), 2.19 (m, 6H, C), 4.37 (t, = 5.6, 4H, C), 4.57 (q, = 5.4, 2H, C), 4.92 (t, = 5.6, 4H, C), 6.86 (m, 4H, Ph), 7.70 (m, 4H, Ph), 8.17 (m, 4H, Ph), 9.95 (s, 2H, benzimiH) (benzimi = benzimidazole)
。
the experimental flow is shown in the following chart:
examples
3
Under the protection of nitrogen, in acetonitrile
(30 mL)
Adding in
1,5-
II
[1-
Ethyl radical
-3
Imidazole ethyl radical
]
Naphthalene diether hexafluorophosphate
(0.200 g, 0.3 mmol)
And silver oxide
(0.096 g, 0.4 mmol)
Refluxing of the suspension
24
And (4) hours. The solution was filtered and concentrated to
5 mL
Adding diethyl ether
(5 mL)
Obtaining a white precipitate, namely
1,5-
II
[1-
Ethyl radical
-3
Imidazole ethyl radical
]
Cyclic compounds of silver naphthalene diethers. Yield:
0.078 g (33%)
. Melting point:
246-247 ˚C
. The method for growing the metal organic complex crystal specifically refers to a method obtained by diffusing diethyl ether into an organic solution of a metal complex at room temperature.
1
Z, 6H NMR (400 MHDMSO-d):
δ
J H 3 J H 2 J H 2 H 2 H H J H 1.40 (t, = 7.2, 12H, C), 4.25 (q, = 7.2, 8H, C), 4.51 (t, = 4.4, 8H, C), 4.76 (t, 8H, C), 7.73-7.78 (m, 12H, Ph), 7.84 (d, 4H, imi), 7.94 (d, = 7.8, 4H, imi).
The experimental flow is shown in the following chart:
the crystal structure is shown in the attached drawings of the specification
1
。
Examples
4
Preparation of the compound and preparation of the compound
5
Similarly, only the compounds
2
Exchange for a Compound
4
. Yield:
0.170 g (45%)
. Melting point:
245-247 ˚C
. The method for growing the metal organic complex crystal specifically refers to a method obtained by diffusing diethyl ether into an organic solution of a metal complex at room temperature.
1
Z, 6H NMR (400 MHDMSO-d):
δ
J H 3 H 2 H 2 J H 2 J H 2 J H 2 J H H J H J H0.76 (t, = 5.6, 12H, C), 1.29 (m, 8H, C), 1.84 (m, 8H, C), 4.23 (t, = 4.2, 8H, C), 4,58 (t, = 5.6, 8H, C), 4.99 (t, = 4.2, 8H, C), 6.40 (s, = 6.4, 8H, Ph), 7.48 (m, 8H, Ph), 7.84 (d, = 6.4, 4H, Ph), 8.05 (d, = 6.4, 4H, Ph).
The experimental flow is shown in the following chart:
the crystal structure is shown in the attached drawings of the specification
2
。
Examples
3
And
4
crystal structure parameters of prepared N-heterocyclic carbene metal silver complex
Examples of the applications
1
Examples of the invention
3
And
4
the prepared cyclic complex crystal is prepared into acetonitrile solution with certain concentration (
1
×
10
－
5
mol/L
). Testing fluorescence by liquids, co-ordinationThe fluorescence emission spectrum intensity of the compound is stronger than that of the corresponding ligand, and the fluorescence change is obvious. In that
298K
Acetonitrile (a)
1
×
10
－
5
mol/L
) Excitation wavelength in solution of
232nm
Drawing of fluorescent quenching medium for molecular recognition of p-phenylenediamine under the condition
3
And
4
。
in summary, the content of the present invention is not limited to the examples, and those skilled in the art can easily suggest other examples within the technical teaching of the present invention, but such examples are included in the scope of the present invention.
Claims (5)
1. An N-heterocyclic carbene cyclic metal complex crystal has the following structural formula:
the crystal structure parameters of the N-heterocyclic carbene metal silver complex measured by an X-ray diffractometer are as follows:
。
2. a process for preparing the azacyclo-carbene cyclic metal complex crystal of claim 1, comprising:
under the protection of inert gas, taking an N-heterocyclic carbene salt and a metal compound which take 1, 5-bis [ 1-substituent-3-imidazole ethyl ] naphthalene diether and 1, 4-bis [ 1-substituent-3-benzimidazole ethyl ] benzene diether as precursors in a molar ratio of 0.5-3: 2-6, dissolving the mixture in a water-removed high-purity organic solvent, reacting at the temperature of 0-100 ℃ for 12-24 hours, filtering, and naturally volatilizing to obtain the carbene cyclic metal complex.
3. The method for producing the azacyclo-carbene cyclic metal complex crystal according to claim 2, wherein the metal compound is silver oxide, silver acetate or silver carbonate.
4. The method for preparing the N-heterocyclic carbene cyclic metal complex crystal as set forth in claim 2, wherein the organic solvent is one or a mixture of more selected from tetrahydrofuran, dichloromethane, trichloromethane, 1, 2-dichloroethane, acetone, diethyl ether, acetonitrile, nitroethane, N-dimethylformamide and dimethyl sulfoxide.
5. Use of the azacyclo-carbene cyclic metal complex crystal according to claim 1 for the preparation of phosphor materials.
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| CN103242300B (en) * | 2013-04-15 | 2014-06-25 | 天津师范大学 | N-heterocyclic carbene metal complex based on quinoxaline as well as preparation method and application thereof |
| CN104140434B (en) * | 2013-05-09 | 2016-08-03 | 南开大学 | Nitrogen heterocyclic carbene silver complex of double pyrazole alkyl functional and preparation method thereof |
| CN104230965B (en) * | 2014-09-04 | 2016-04-06 | 天津师范大学 | The preparation of ring-type silver complex and the application in identification object thereof |
| CN104910076B (en) * | 2015-05-13 | 2017-03-01 | 天津师范大学 | The preparation of bis-benzimidazole salt and its application in intramolecular coupling reaction |
| CN105646360A (en) * | 2016-01-15 | 2016-06-08 | 天津师范大学 | N-heterocyclic carbene metal complex based on binaphthol link and preparation method and application thereof |
| CN105541876B (en) * | 2016-01-15 | 2017-07-11 | 天津师范大学 | N-heterocyclic carbine metal complex of anthraquinone bridging and preparation method and application |
| CN112169836A (en) * | 2020-09-28 | 2021-01-05 | 广东石油化工学院 | Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same |
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| US3853907A (en) * | 1971-10-14 | 1974-12-10 | Ici Ltd | Antibacterial bis(imidazolium quaternary salts) |
| WO2010025558A1 (en) * | 2008-09-05 | 2010-03-11 | University Haealth Network | Triazolium and imidazolium salts and uses thereof as antimalarials |
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| US3853907A (en) * | 1971-10-14 | 1974-12-10 | Ici Ltd | Antibacterial bis(imidazolium quaternary salts) |
| WO2010025558A1 (en) * | 2008-09-05 | 2010-03-11 | University Haealth Network | Triazolium and imidazolium salts and uses thereof as antimalarials |
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| 杨晓琼等.《Crystallic Structure of N-Heterocyclic Carbene Silver(Ⅰ) Complex with Fluorescence》.《第十六届全国金属有机化学学术讨论会论文集》.2010,369. * |
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