CN115215852A - 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用 - Google Patents
中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用 Download PDFInfo
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- CN115215852A CN115215852A CN202110403546.1A CN202110403546A CN115215852A CN 115215852 A CN115215852 A CN 115215852A CN 202110403546 A CN202110403546 A CN 202110403546A CN 115215852 A CN115215852 A CN 115215852A
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- palladium
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 125000003003 spiro group Chemical group 0.000 title claims abstract description 35
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- -1 hydroxy, mercapto Chemical class 0.000 claims description 43
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004414 alkyl thio group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 8
- 125000004986 diarylamino group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000003106 haloaryl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000005216 haloheteroaryl group Chemical group 0.000 claims description 8
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 8
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000002527 isonitriles Chemical class 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 8
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 8
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 7
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 7
- 125000002837 carbocyclic group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 abstract description 56
- 150000004696 coordination complex Chemical class 0.000 abstract description 19
- 230000010287 polarization Effects 0.000 abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 abstract description 9
- 239000012634 fragment Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 100
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 62
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000003208 petroleum Substances 0.000 description 27
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 19
- 239000012074 organic phase Substances 0.000 description 19
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- 239000012267 brine Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000004020 luminiscence type Methods 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 230000005587 bubbling Effects 0.000 description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 description 8
- 235000011009 potassium phosphates Nutrition 0.000 description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
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- 230000002194 synthesizing effect Effects 0.000 description 7
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- 150000001875 compounds Chemical class 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
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- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- STXAVEHFKAXGOX-UHFFFAOYSA-N 3-bromobenzonitrile Chemical compound BrC1=CC=CC(C#N)=C1 STXAVEHFKAXGOX-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000005092 sublimation method Methods 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- LOPKSXMQWBYUOI-DTWKUNHWSA-N (1r,2s)-1-amino-2,3-dihydro-1h-inden-2-ol Chemical compound C1=CC=C2[C@@H](N)[C@@H](O)CC2=C1 LOPKSXMQWBYUOI-DTWKUNHWSA-N 0.000 description 1
- LOPKSXMQWBYUOI-BDAKNGLRSA-N (1s,2r)-1-amino-2,3-dihydro-1h-inden-2-ol Chemical compound C1=CC=C2[C@H](N)[C@H](O)CC2=C1 LOPKSXMQWBYUOI-BDAKNGLRSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 238000012984 biological imaging Methods 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 238000001437 electrospray ionisation time-of-flight quadrupole detection Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
- C07D263/64—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings linked in positions 2 and 2' by chains containing six-membered aromatic rings or ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
本发明公开了一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。所述螺手性金属配合物分子可通过四齿配体中的中心手性片段La可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位,形成光学纯的的螺手性金属配合物圆偏振光发光材料,无需手性拆分,且材料具有高的化学稳定性和热稳定性,在圆偏振发光元件中具有重要应用。
Description
技术领域
本发明涉及一种圆偏振发光材料及其应用,尤其涉及一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。
背景技术
圆偏振发光(CPL)是由手性发光物质受到激发后发射出左旋或右旋的圆偏振光的现象,因此,手性发光材料的设计发展是此领域的关键。随着科研人员的深入研究,到目前为止,圆偏振发光材料在3D显示、数据存储、量子计算、光学防伪、生物成像及不对称合成等领域具有重要应用。
环金属铂(II)和钯(II)配合物磷光材料由于其重原子效应可以充分利用电致激发产生的所有单线态和三线态激子,使其最大理论量子效率可高达100%,所以此类配合物是一类理想的发光材料。双齿环金属铂(II)和钯(II)配合物刚性较低,由于两个双齿配体易扭曲、振动从而使激发态材料分子的能量以非辐射方式消耗,致使其发光量子效率降低(Inorg.Chem.2002,41,3055);虽然基于三齿配体的环金属铂(II)和钯(II)配合物由于其分子刚性增强可以提高发光量子效率(Inorg.Chem.2010,49,11276),但是所含有的第二个单齿配体(如Cl-、苯氧基负离子、炔负离子、卡宾等)会使配合物的化学稳定性和热稳定性大大降低,难以升华提纯用于OLED器件的制备;所以基于双齿和三齿配体环金属配合物发光材料均不利于其在稳定高效OLED器件方面是应用。二价环金属铂(II)和钯(II)配合物中心金属离子均为dsp2杂化,易于和四齿配体配位形成稳定而刚性的平面四边形构型分子;高的分子刚性可抑制由于分子振动和转动所引起的非辐射弛豫,减少激发态材料分子的能量损失,因此利于材料分子发光量子效率的提高。由于环金属铂(II)和钯(II)配合物四齿配体末端两个芳基的位阻,使材料分子呈现出扭曲的四边形构型(Chem.Mater.2020,32,537),理论上具有螺手性的性质,但是分子在溶液中或加热升华过程中极易通过配体末端两个芳基的上下振动而消旋,无法分离其对映异构体,极难得到光学纯的环金属铂(II)和钯(II)配合物材料分子,使其不具有圆偏振发光的性质。因此,如何设计和发展具有高化学稳定性和热稳定性,且兼具圆偏振发光性质的光学纯环金属铂(II)和钯(II)配合物材料分子对于其在圆偏振发光OLED器件(CP-OLED)中的应用具有重要意义和巨大实用价值,也是CP-OLED领域急需解决的问题。
发明内容
本发明的目的是针对现有技术不足,提供了一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料及应用。所述螺手性金属配合物分子可通过四齿配体中的中心手性片段La可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位,形成光学纯的的螺手性金属配合物圆偏振光发光材料,无需手性拆分,且材料具有高的化学稳定性和热稳定性,在圆偏振发光元件中具有重要应用。
本发明的目的是通过以下技术方案来实现的:
一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料,其特征在于,其化学式如通式(I)、(I')、(II)、(II')、(III)和(III')所示,其中(I)和(I')、(II)和(II')、(III)和(III')互为对映异构体:
其中M为Pt或Pd;V1、V2、V3和V4各自独立的为N或C;
L1、L2和L3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环;La和Lb是各自独立的为五元中心手性碳环或者杂环;由于La和L1、La和Lb之间的空间位阻,使整个金属配合物为非平面构型,且中心手性La可自主以空间位阻小的方式诱导以金属为中心的螺手性四齿环金属铂(II)和钯(II)配合物的形成;
A1、A2、X和X1各自独立地为O、S、CRxRy、C=O、SiRxRy、GeRxRy、NRz、PRz、RzP=O、
AsRz、RzAs=O、S=O、SO2、Se、Se=O、SeO2、BH、BRz、RzBi=O或BiRz;
R1、R2和R3各自独立地表示单、双、三、或四-取代或者无取代,同时R1、R2、R3、Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Rx、Ry和Rz各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的R1、R2和R3可以选择性连接形成稠环;Ra、Rb、Rc和Rd中的任意两个基团可连接形成环状体系,Re、Rf、Rg和Rh中的任意两个基团可连接形成环状体系。
上述具有通式(I)、(I')、(II)和(II')的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料,可为如下通式(I-A)、(I-A)、(I-B)、(I-C)、(I-D)、(I-E)、(I-F)、(I-G)、(I-H)、(I-I)、(II-A)和其对映异构体(I'-A)、(I'-A)、(I'-B)、(I'-C)、(I'-D)、(I'-E)、(I'-F)、(I'-G)、(I'-H)、(I'-I)、(II'-A)之一,但不局限于此:
其中M为Pt或Pd;V1、V2、V3和V4各自独立的为N或C;
L1、L2和L3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环;La为五元中心手性碳环或者杂环;由于La和L1之间的空间位阻,使整个金属配合物为非平面构型,且由中心手性La可自主以空间位阻小的方式诱导以金属为中心的螺手性四齿环金属铂(II)和钯(II)配合物的形成;
A1、X、Z和Z1各自独立地为O、S、CRxRy、C=O、SiRxRy、GeRxRy、NRz、PRz、RzP=O、AsRz、RzAs=O、S=O、SO2、Se、Se=O、SeO2、BH、BRz、RzBi=O或BiRz;
R1、R2、R3、R4和R5各自独立地表示单、双、三、或四-取代或者无取代,同时R1、R2、R3、R3、R4、R5、Ra、Rb、Rc、Rd、Rx、Ry和Rz各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的R1、R2、R3、R4和R5可以选择性连接形成稠环;Ra、Rb、Rc和Rd中的任意两个基团可连接形成环状体系。
上述中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料通式结构中的La和Lb可为如下结构,但不局限于此:
其中Ra1、Ra2和Ra3各自独立地表示氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;
其中Rb1、Rc1和Rc2各自独立地表示单、双、三、或四-取代或者无取代,同时Rb1、Rc1和Rc2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的Rb1、Rc1和Rc2可以选择性连接形成稠环。
上述的La和Lb可进一步具体为如下结构,但不局限于此:
进一步地,中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料在有机发光元件中的应用。所述有机发光元件,其为有机发光二极管、发光二极管或发光电化学电池。
所述发光元件包括第一电极、第二电极及设置于所述第一电极和所述第二电极之间的至少一个有机层,所述有机层包括中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料。
本发明的有益效果是:
(1)中心手性自主诱导螺手性的产生:通过设计和发展具有中心手性La的四齿配体,利用其和另一末端配体L1或Lb之间的空间位阻效应,使整个四齿环金属环金属铂(II)和钯(II)配合物分子为扭曲的四边形构型;同时,中心手性La可自主诱导整个四齿配体以空间位阻小的方式和金属离子配位,形成光学纯的以金属离子为中心的螺手性四齿环金属铂(II)和钯(II)配合物圆偏振光发光材料。如附图1所示。
(2)光学纯原料经济易得:制备含有中心手性La四齿配体所需要的两个手性光学纯对应异构体均为商业化经济易得的化合物,便于大量制备两个手性光学纯的四齿配体。
(3)圆偏振光发光材料无需手性拆分:由上述两个手性光学纯的四齿配体可以方便制备螺手性四齿环金属铂(II)和钯(II)配合物的两个手性光学纯的对应异构体圆偏振光发光材料,无需通过手性柱分离纯化,大大降低材料的制备成本。
(4)材料化学稳定性和热稳定性高:所设计发展的四齿配体可以和dsp2杂化的铂(II)和钯(II)金属离子很好的配位形成稳定而刚性的四边形构型分子,化学稳定性高;同时,由于所设计的中心手性配体La和另一末端配体L1或Lb之间具有较大空间位阻效应,使整个金属配合物分子可形成稳定的螺手性四齿环金属配合物,使其在溶液或高温升华过程中均不会发生消旋而丧失圆偏振发光性质。
附图说明
图1为光学纯的以金属离子为中心的螺手性四齿环金属配合物圆偏振光发光材料设计思路图;
图2中,图(A)为光学纯螺手性材料(R,S)-M-PtLA1的X-衍射单晶结构正视图,图(B)为光学纯螺手性材料(R,S)-M-PtLA1的X-衍射单晶结构俯视图,图(C)为通过密度泛函理论(DFT)计算优化后的(R,S)-M-PtLA1分子结构正视图,图(D)为通过密度泛函理论(DFT)计算优化后的(R,S)-M-PtLA1分子结构俯视图,图(E)为DFT计算优化后的(S,R)-P-PtLA1的分子结构正视图,图(F)为DFT计算优化后的(S,R)-P-PtLA1的分子结构俯视图;
图3中,图(A)为通过DFT计算优化后的(R,S)-M-PtLB3的分子结构正视图,图(B)为通过DFT计算优化后的(R,S)-M-PtLB3的分子结构俯视图,图(C)为(R,S)-M-PtLB3的分子结构式,图(D)为通过DFT计算优化后的(S,R)-P-PtLB3的分子结构正视图,图(E)为通过DFT计算优化后的(S,R)-P-PtLB3的分子结构俯视图,图(F)为(S,R)-P-PtLB3的分子结构式;
图4中,图(A)为通过DFT计算优化后的(R,S)-M-PtLH1的分子结构正视图,图(B)为通过DFT计算优化后的(R,S)-M-PtLH1的分子结构俯视图,图(C)为(R,S)-M-PtLH1的分子结构式,图(D)为通过DFT计算优化后的(S,R)-P-PtL H1的分子结构正视图,图(E)为通过DFT计算优化后的(S,R)-P-PtL H1的分子结构俯视图,图(F)为(S,R)-P-PtL H1的分子结构式;
图5中,图(A)为通过DFT计算优化后的M-PtLIII-1的分子结构正视图,图(B)为M-PtLIII-1的分子结构式,图(C)为通过DFT计算优化后的P-PtLIII-1的分子结构正视图,图(D)为P-PtLIII-1的分子结构式;
图6为光学纯(R,S)-M-PtLA1和(S,R)-P-PtLA1在二氯甲烷溶液中室温下的发射光谱图;
图7为光学纯(R,S)-M-PtLA2和(S,R)-P-PtLA2在二氯甲烷溶液中室温下的发射光谱图;
图8为光学纯(R,S)-M-PtLA3和(S,R)-P-PtLA3在二氯甲烷溶液中室温下的发射光谱图;
图9为光学纯(R,S)-M-PtLAN和(S,R)-P-PtLAN在二氯甲烷溶液中室温下的发射光谱图;
图10为光学纯(R,S)-M-PtLH1和(S,R)-P-PtLH1在二氯甲烷溶液中室温下的发射光谱图;
图11为光学纯(S,R)-P-PtLC3和P-PtLIII-1在二氯甲烷溶液中室温下的发射光谱图;
图12为(S,R)-P-PtLA1和(R,S)-M-PtLA1在二氯甲烷溶液中的圆二色光谱图;
图13为有机发光元件的结构示意图。
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。
下面举例说明上述通式中所代表的本发明的圆偏振光发光材料的具体实例,然而,不解释为限制本发明。
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(CDCl3)或氘代二甲基亚砜(DMSO-d6)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CDCl3作溶剂,则氢谱和碳谱分别以TMS(δ=0.00ppm)和CDCl3(δ=77.00ppm)作为内标。如果用DMSO-d6作溶剂,则氢谱和碳谱分别以TMS(δ=0.00ppm)和DMSO-d6(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(S,R)-P-PtLA1合成路线如下:
(1)中间体1-Br的合成:向带有磁力转子的单口瓶中依次加入间溴苯甲腈(10g,54.94mmol,1.0当量),甲醇钠(297mg,5.49mmol,0.1当量),室温搅拌,反应1天。加乙酸至固体消失,减压蒸馏除去溶剂,得粗品A,加入(1S,2R)-1-氨基2,3-二氢-1H-茚-2-醇(4.10g,27.47mmol,0.5当量),无水乙醇(30mL),该混合物在85℃的油浴中搅拌反应1.5天,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,淋洗剂:石油醚/乙酸乙酯=50:1-10:1,得到产物1-Br,白色固体5.60g,收率65%。1H NMR(500MHz,CDCl3):δ3.40(d,J=18.0Hz,1H),3.51-3.56(m,1H),5.57(t,J=7.5Hz,1H),7.79(d,J=8.0Hz,1H),7.26-7.31(m,4H),7.59-7.63(m,2H),7.96(d,J=8.0Hz,1H),8.12(t,J=2.0Hz,1H)。
(2)中间体4-OH的合成:向带有磁力转子的干燥封管中依次加入手性溴(1.5g,4.77mmol,1.0当量),氯化亚铜(24mg,0.24mmol,5mol%),配体1(87mg,0.24mmol,5mol%)和叔丁醇钠(917mg,9.55mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(8mL),去离子水(2mL)。将封管置于110℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加稀盐酸调至中性或弱酸性,再加碳酸氢钠调至弱碱性,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物4-OH,棕色固体934mg,收率78%。1H NMR(500MHz,DMSO-d6):δ3.22(d,J=18.0Hz,1H),3.46-3.51(m,1H),5.47-5.50(m,1H),5.68(d,J=8.0Hz,1H),6.87-6.90(m,1H),7.21-7.3(m,6H),7.43-7.44(m,1H),9.67(s,1H)。
(3)中间体手性2-Br的合成:向带有磁力转子的单口瓶中依次加入间溴苯甲腈(10g,54.94mmol,1.0当量),甲醇钠(297mg,5.49mmol,0.1当量),室温搅拌,反应1天。加乙酸至固体消失,减压蒸馏除去溶剂,得粗品A,加入(1R,2S)-1-氨基2,3-二氢-1H-茚-2-醇(3.28g,21.97mmol,0.4当量),无水乙醇(30mL),该混合物在85℃的油浴中搅拌反应1.5天,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,淋洗剂:石油醚/乙酸乙酯=50:1-10:1,得到产物2-Br,白色固体5.74g,收率83%。1H NMR(500MHz,CDCl3):δ3.41(d,J=18.5Hz,1H),3.52-3.57(m,1H),5.59(s,1H),5.81(d,J=3.0Hz,1H),7.27-7.31(m,4H),7.60-7.65(m,2H),7.98-8.00(m,1H),8.13(s,1H)。
(4)配体(S,R)-LA1的合成:向带有磁力转子的干燥封管中依次加入1-Br(579mg,1.84mmol,1.2当量),1-OH(400mg,1.54mmol,1.0当量),碘化亚铜(29mg,0.15mmol,10mol%),配体2(50mg,0.15mmol,10mol%)和磷酸钾(654mg,3.08mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(10mL)。将封管置于90℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到配体(S,R)-LA1,白色固体533mg,收率70%。1HNMR(500MHz,DMSO-d6):δ3.19(d,J=17.5Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1H),5.65(d,J=7.5Hz,1H),7.03(dd,J=8.5,2.5Hz,1H),7.19-7.28(m,4H),7.35-7.40(m,3H),7.42-7.47(m,3H),7.50(d,J=2.0Hz,1H),7.57-7.59(m,1H),7.76-7.79(m,2H),8.04-8.07(m,1H),8.23(d,J=7.5Hz,1H),8.27(d,J=8.0Hz,1H),8.65-8.66(m,1H)。
(5)(S,R)-P-PtLA1的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA1(150mg,0.30mmol,1.0当量),氯亚铂酸钾(132mg,0.32mmol,1.05当量),四正丁基溴化铵(10mg,0.030mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(25mL)。反应液氮气鼓泡30分钟后,室温先搅拌12小时,然后在100℃下搅拌反应2天,冷却至室温,减压蒸馏除去溶剂,加入氯化亚锡(114mg,0.6mmol,2.0当量),二氯甲烷(30mL),室温搅拌1天。反应液水洗,水相用二氯甲烷萃取三次,合并有机相,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=1:1,得到产物(S,R)-P-PtLA1,淡黄色固体126mg,收率60%。1H NMR(500MHz,DMSO-d6):δ3.49(d,J=18.5Hz,1H),3.62-3.67(m,1H),6.05(t,J=7.5Hz,1H),6.26(d,J=7.5Hz,1H),7.01(d,J=7.5Hz,1H),7.10(t,J=7.5Hz,1H),7.12-7.18(m,3H),7.20-7.24(m,2H),7.35(d,J=7.5Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J=8.0Hz,1H),8.15-8.17(m,1H),8.20(d,J=8.5Hz,1H),8.26-8.29(m,1H),8.36(d,J=8.5Hz,1H),9.57(dd,J=6.0,1.5Hz,1H)。
实施例2:四齿环金属铂(II)配合物(R,S)-M-PtLA1的合成:
(1)配体(R,S)-LA1的合成:向带有磁力转子的干燥封管中依次加入2-Br(3.19g,10.14mmol,1.2当量),1-OH(2.20g,8.45mmol,1.0当量),碘化亚铜(29mg,0.84mmol,10mol%),配体2(276mg,0.84mmol,10mol%)和磷酸钾(3.59g,16.90mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(40mL)。将封管置于100℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物(R,S)-LA1,白色固体2.12g,收率51%。1H NMR(500MHz,DMSO-d6):δ3.19(d,J=18.0Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1H),5.65(d,J=7.5Hz,1H),7.03(dd,J=7.5,2.0Hz,1H),7.19-7.28(m,4H),7.34-7.40(m,3H),7.43-7.48(m,3H),7.50(d,J=2.0Hz,1H),7.57-7.59(m,1H),7.77-7.79(m,2H),8.04-8.08(m,1H),8.24(d,J=8.0Hz,1H),8.28(d,J=8.5Hz,1H),8.65-8.67(m,1H)。
(2)(R,S)-M-PtLA1的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA1(900mg,1.82mmol,1.0当量),氯亚铂酸钾(795mg,1.92mmol,1.05当量),四正丁基溴化铵(59mg,0.182mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(110mL)。反应液氮气鼓泡30分钟后,室温先搅拌12小时,然后在100℃下搅拌反应2天,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,淋洗剂:石油醚/二氯甲烷=1:1,得到产物(R,S)-M-PtLA1,淡黄色固体1.01g,收率81%。1H NMR(500MHz,DMSO-d6):δ3.49(d,J=18.0Hz,1H),3.62-3.67(m,1H),6.04(t,J=7.0Hz,1H),6.27(d,J=7.0Hz,1H),7.01(d,J=8.0Hz,1H),7.10(t,J=7.0Hz,1H),7.12-7.18(m,3H),7.21-7.24(m,2H),7.35(d,J=7.0Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J=8.5Hz,1H),8.16-8.18(m,1H),8.20(d,J=8.5Hz,1H),8.26-8.30(m,1H),8.37(d,J=8.5Hz,1H),9.57(m,1H)。
实施例3:四齿环金属铂(II)配合物(S,R)-P-PtLA2的合成:
(1)配体(S,R)-LA2的合成:向带有磁力转子的干燥封管中依次加入1-Br(1.82g,5.80mmol,1.2当量),2-OH(1.50g,4.83mmol,1.0当量),碘化亚铜(91mg,0.48mmol,10mol%),配体2(157mg,0.48mmol,10mol%)和磷酸钾(2.05g,9.05mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(30mL)。将封管置于100℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=20:1-5:1,得到产物(S,R)-LA2,棕色固体1.63g,收率62%。1H NMR(600MHz,CDCl3):δ3.45(d,J=18.6Hz,1H),3.53-3.56(m,1H),5.66-5.69(m,1H),5.88(s,1H),7.01(dd,J=8.4,1.8Hz,1H),7.24-7.31(m,6H),7.35-7.40(m,2H),7.44-7.47(m,1H),7.56-7.59(m,1H),7.63(t,J=1.8Hz,1H),7.70(d,8.4Hz,1H),7.73-7.75(m,1H),7.77(d,J=8.0Hz,1H),7.87-7.88(m,1H),7.97(d,J=8.4Hz,1H)。8.07(d,J=8.4Hz,1H),8.08-8.10(m,2H),8.32(d,J=8.0Hz,1H)。
(2)(S,R)-P-PtLA2的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA2(200mg,0.37mmol,1.0当量),氯亚铂酸钾(161mg,0.39mmol,1.05当量),四正丁基溴化铵(12mg,0.037mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后,先室温搅拌12小时,然后在120℃下搅拌反应2天,冷却至室温,减压蒸馏除去溶剂,加入氯化亚锡(140mg,0.74mmol,2.0当量),二氯甲烷(30mL),室温搅拌1天。反应液水洗,水相用二氯甲烷萃取三次,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,淋洗剂:石油醚/二氯甲烷=1:1,得到产物(S,R)-P-PtLA2,淡黄色固体101mg,收率37%。1H NMR(600MHz,DMSO-d6):δ3.47(d,J=18.0Hz,1H),3.49-3.51(m,1H),5.12(d,J=7.8Hz,1H),5.32(d,J=4.8Hz,1H),5.93-5.95(m,1H),6.05(d,J=8.4Hz,1H),6.93(d,J=7.2Hz,1H),7.10(t,J=7.2Hz,1H),7.15(t,J=8.4Hz,1H),7.17-7.18(m,1H),7.21(d,J=7.2Hz,1H),7.23-7.25(m,1H),7.45(t,J=7.8Hz,1H),7.53-7.56(m,1H),7.66-7.69(m,1H),7.78(d,J=8.4Hz,1H),8.04-8.06(m,1H),8.13(dd,J=7.8,1.2Hz,1H),8.18(dd,J=7.8,1.2Hz,1H),8.36(d,J=7.8Hz,1H),8.66(d,J=9.0Hz,1H),8.82(d,J=9.0Hz,1H),9.40(d,J=8.4Hz,1H)。
实施例4:四齿环金属铂(II)配合物(R,S)-M-PtLA2的合成:
(1)配体(R,S)-LA2的合成:向带有磁力转子的干燥封管中依次加入2-Br(1.38g,4.40mmol,1.2当量),2-OH(1.14g,3.67mmol,1.0当量),碘化亚铜(70mg,0.37mmol,10mol%),配体2(121mg,0.37mmol,10mol%)和磷酸钾(1.56g,7.34mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。将封管置于90℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物(R,S)-LA2,白色固体1.23g,收率62%。1HNMR(500MHz,CDCl3):δ3.44(d,J=18.0Hz,1H),3.53-3.58(m,1H),5.66-5.70(m,1H),5.85-5.88(m,1H),7.01(dd,J=8.0,2.0Hz,1H),7.24-7.31(m,6H),7.35-7.47(m,3H),7.56-7.59(m,1H),7.62(t,J=2.0Hz,1H),7.70(d,J=2.0Hz,1H),7.72-7.78(m,2H),7.88(d,J=7.5Hz,1H),7.96(d,J=8.0Hz,1H),8.06-8.10(m,3H),8.31(d,J=8.5Hz,1H)。
(2)(R,S)-M-PtLA2的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA2(200mg,0.37mmol,1.0当量),氯亚铂酸钾(161mg,0.39mmol,1.05当量),四正丁基溴化铵(12mg,0.037mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后,先室温搅拌12小时,然后在110℃下搅拌反应2天,冷却至室温,减压蒸馏除去溶剂,加入氯化亚锡(140mg,0.74mmol,2.0当量),二氯甲烷(30mL),室温搅拌1天。反应液水洗,水相用二氯甲烷萃取三次,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,淋洗剂:石油醚/二氯甲烷=1:1,得到产物(R,S)-M-PtLA2,淡黄色固体119mg,收率44%。1H NMR(500MHz,DMSO-d6):δ3.29-3.34(m,1H),3.45-3.50(m,1H),5.12(d,J=7.5Hz,1H),5.94(d,J=7.0Hz,1H),6.04(d,J=8.0Hz,1H),6.94(t,J=7.5Hz,1H),7.10(t,J=7.5Hz,1H),7.15(d,J=8.0Hz,1H),7.17-7.21(m,3H),7.23-7.25(m,1H),7.45(t,J=7.5Hz,1H),7.53-7.56(m,1H),7.68(t,J=7.0Hz,1H),7.78(d,J=8.0Hz,1H),8.04-8.07(m,1H),8.12-8.14(m,1H),8.17-8.19(m,1H),8.36(d,J=8.0Hz,1H),8.66(d,J=9.5Hz,1H),8.82(d,J=9.5Hz,1H),9.40(d,J=8.5Hz,1H)。
实施例5:四齿环金属铂(II)配合物(S,R)-P-PtLA3的合成:
(1)配体(S,R)-LA3合成:向带有磁力转子的干燥封管中依次加入1-Br(477mg,1.52mmol,1.2当量),3-OH(400mg,1.27mmol,1.0当量),碘化亚铜(25mg,0.13mmol,10mol%),配体2(43mg,0.13mmol,10mol%)和磷酸钾(539mg,2.54mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(10mL)。将封管置于100℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/二氯甲烷/乙酸乙酯=5:1:1,得到产物(S,R)-LA3,棕色固体412mg,收率59%。1H NMR(500MHz,CDCl3):δ1.83-1.94(m,4H),2.82(t,J=6.0Hz,2H),2.94(d,J=6.5Hz,2H),3.31-3.35(d,J=17.5Hz,1H),3.44-3.49(m,1H),5.43-5.46(m,1H),5.71(d,J=8.0Hz,1H),6.96(dd,J=8.5,2.5Hz,1H),7.11-7.14(m,1H),7.24-7.27(m,7H),7.28-7.30(m,2H),7.32(d,J=8.0Hz,1H),7.37-7.41(dd,J=3.0,1.5Hz,1H),7.65-7.67(m,1H),7.77(d,J=6.0Hz,1H),8.02-8.06(m,2H)。
(2)(S,R)-P-PtLA3的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LA3(200mg,0.37mmol,1.0当量),氯亚铂酸钾(161mg,0.39mmol,1.05当量),四正丁基溴化铵(12mg,0.037mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后,先室温搅拌12小时,然后在120℃下搅拌反应2天,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,淋洗剂:石油醚/二氯甲烷=1:1-1:2,得到产物(S,R)-P-PtLA3,淡黄色固体134mg,收率49%。1H NMR(400MHz,CDCl3):δ1.83-1.91(m,2H),2.85-2.92(m,4H),2.94(d,J=6.5Hz,2H),3.41-3.46(d,J=19.6Hz,1H),3.53-3.59(m,1H),5.61(d,J=7.6Hz,1H),5.65-5.69(m,1H),6.96-7.00(m,1H),7.08-7.17(m,2H),7.15-7.31(m,6H),7.36-7.40(m,2H),7.57-7.62(m 1H),7.91-7.96(m,2H),8.11-8.13(m,1H)。
实施例6:四齿环金属铂(II)配合物(R,S)-M-PtLA3的合成:
(1)配体(R,S)-LA3的合成:向带有磁力转子的干燥封管中依次加入2-Br(477mg,1.52mmol,1.2当量),3-OH(400mg,1.27mmol,1.0当量),碘化亚铜(25mg,0.13mmol,10mol%),配体2(43mg,0.13mmol,10mol%)和磷酸钾(539mg,2.54mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(10mL)。将封管置于100℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/二氯甲烷/乙酸乙酯=5:1:1,得到产物(R,S)-M-LA3,棕色固体392mg,收率56%。1H NMR(500MHz,CDCl3):δ1.86-1.93(m,4H),2.84(t,J=7.5Hz,2H),2.94(d,J=6.5Hz,2H),3.41(d,J=18.0Hz,1H),3.49-3.55(m,1H),5.61-5.66(m,1H),5.77-5.82(m,1H),6.94-6.96(m,1H),7.24-7.27(m,7H),7.28-7.31(m,2H),7.37-7.42(m,2H),7.52-7.55(m,1H),7.56-7.58(m,1H),7.73(d,J=8.5Hz,1H),8.03-8.06(m,2H)。
(2)(R,S)-PtLA3的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(R,S)-LA3(200mg,0.37mmol,1.0当量),氯亚铂酸钾(161mg,0.39mmol,1.05当量),四正丁基溴化铵(12mg,0.037mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后,先室温搅拌12小时,然后在120℃下搅拌反应2天,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,淋洗剂:石油醚/二氯甲烷=1:1-1:2,得到产物(R,S)-M-PtLA3,淡黄色固体128mg,收率47%。δ1.88-1.93(m,4H),2.84-2.94(m,4H),3.55(d,J=18.0Hz,1H),3.56-3.61(m,1H),5.62(d,J=7.5Hz,1H),5.85-5.88(m,1H),6.68(d,J=7.5Hz,1H),6.99-7.01(m,1H),7.01-7.13(m,1H),7.18-7.24(m,5H),7.31-7.35(m,1H),7.37-7.41(m,1H),7.60(d,J=8.0Hz,1H),7.68(d,J=8.0Hz,1H),7.93-7.98(m,2H),8.13-8.14(d,J=8.5Hz,1H)。
实施例7:四齿环金属铂(II)配合物(S,R)-P-PtLC1的合成:
(1)配体(S,R)-LC1的合成:向带有磁力转子的干燥封管中依次加入3-Br(859mg,2.35mmol,1.5当量),4-OH(400mg,1.59mmol,1.0当量),碘化亚铜(37mg,0.20mmol,10mol%),配体2(65mg,0.20mmol,10mol%)和磷酸钾(832mg,3.92mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(15mL)。将封管置于90℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=5:1-3:1,得到产物(S,R)-LC1,白色固体421mg,收率49%。1HNMR(500MHz,DMSO-d6):δ1.61(s,6H),3.22(d,J=18.0Hz,1H),3.45-3.47(m,1H),5.49-5.52(m,1H),5.68(d,J=8.0Hz,1H),6.05(d,J=2.5Hz,1H),6.36(dd,J=8.0,1.5Hz 1H),6.59(dd,J=8.5,2.5Hz 1H),6.98-7.05(m,2H),7.10-7.12(m,1H),7.22-7.31(m,4H),7.35-7.44(m,4H),7.49-7.53(m,2H),7.55-7.57(m,1H),7.89-7.92(m,1H),8.57-8.59(m,J=8.0Hz,1H)。
(2)(S,R)-P-PtLC1的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入(S,R)-LC1(200mg,0.37mmol,1.0当量),氯亚铂酸钾(163mg,0.39mmol,1.05当量),四正丁基溴化铵(12mg,0.037mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(22mL)。反应液氮气鼓泡30分钟后,室温先搅拌12小时,然后在100℃下搅拌反应2天,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,淋洗剂:石油醚/二氯甲烷=1:1,得到产物(S,R)-P-PtLC1,淡黄色固体130mg,收率48%。1H NMR(500MHz,DMSO-d6):δ1.34(s,3H),1.89(s,3H),3.56(d,J=18.5Hz,1H),3.62-3.67(m,1H),6.16-6.20(m,1H),5.47(t,J=8.0Hz,1H),6.94(d,J=8.5Hz,1H),7.09(t,J=7.5Hz 1H),7.21(dd,J=8.0,1.0Hz,1H),7.23(dd,J=7.5,1.5Hz,1H),7.24-7.31(m,4H),7.32-7.34(m,2H),7.39-7.42(m,2H),7.44-7.47(m,2H),7.56(dd,J=7.5,1.5Hz,1H),8.10-8.13(m,1H),9.24(dd,J=6.5,2.0Hz,1H)。
实施例8:四齿环金属铂(II)配合物(S,R)-P-PtLAN的合成:
(1)配体(S,R)-LAN的合成:向带有磁力搅转子的反应管中依次加入1-Br(528mg,1.68mmol,1.2当量),1-NH(548mg,1.40mmol,1.0当量),三(二亚苄基丙酮)二钯(39mg,0.042mmol,3mol%),2-(二叔丁基膦)联苯(13mg,0.032mmol,8mol%),叔丁醇钠(404mg,4.2mmol,3.0当量),然后抽换氮气三次,在氮气保护下加入甲苯(10mL)。随后在110℃的油浴锅中搅拌反应25小时,冷却至室温,减压蒸馏除去溶剂,得到粗品。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯的体积比为6:1-2:1,得到产物(S,R)-P-LAN泡沫状固体599mg,收率68%。1H NMR(400MHz,DMSO-d6):δ1.27(s,9H),3.13-3.18(m,1H),3.44-3.45(m,1H),5.44(t,J=6.0Hz,1H),5.62(d,J=7.6Hz,1H),6.95(d,J=7.6Hz,1H),7.00(d,J=7.6Hz,2H),7.10(d,J=7.6Hz,1H),7.19-7.25(m,3H),7.29-7.38(m,7H),7.41-7.43(m,2H),7.51(s,1H),7.62(d,J=8.0Hz,1H),7.74(d,J=8.0Hz,1H),7.90(t,J=8.0Hz,1H),8.13-8.15(m,2H),8.55(s,1H)。
(2)(S,R)-P-PtLAN的合成:向带有磁力搅转子的三口烧瓶中,依次加入(S,R)-P-LAN(187mg,0.30mmol,1.0当量),二氯化铂(84mg,0.315mmol,1.05当量),然后抽换氮气三次,在氮气保护下加入苯甲腈(18mL)。随后在180℃的油浴锅中搅拌反应18小时,冷却至室温,减压蒸馏除去溶剂,得到粗品。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷的体积比为4:1-2:1,得到产物(S,R)-P-PtLAN红色固体91mg,收率37%。1H NMR(400MHz,DMSO-d6):δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J=6.8Hz,1H),6.19(d,J=7.2Hz,1H),6.26(d,J=8.0Hz,1H),6.32(d,J=8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J=7.2Hz,1H),7.08(t,J=7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J=8.8Hz,1H),7.69(d,J=8.0Hz,2H),7.99(d,J=7.6Hz,1H),8.15(d,J=8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J=5.2Hz,1H)。
实施例9:四齿环金属铂(II)配合物(R,S)-M-PtLAN的合成:
(1)配体(R,S)-LAN的合成:向带有磁力搅转子的反应管中依次加入1-Br(528mg,1.68mmol,1.2当量),1-NH(548mg,1.40mmol,1.0当量),三(二亚苄基丙酮)二钯(39mg,0.042mmol,3mol%),2-(二叔丁基膦)联苯(13mg,0.032mmol,8mol%),叔丁醇钠(404mg,4.2mmol,3.0当量),然后抽换氮气三次,在氮气保护下加入甲苯(10mL)。随后在110℃的油浴锅中搅拌反应25小时,冷却至室温,减压蒸馏除去溶剂,得到粗品。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯的体积比为6:1-2:1,得到产物(R,S)-M-LAN泡沫状固体608mg,收率69%。1H NMR(400MHz,DMSO-d6):δ1.27(s,9H),3.14-3.18(m,1H),3.44-3.46(m,1H),5.44(t,J=7.2Hz,1H),5.62(d,J=7.6Hz,1H),6.95(d,J=8.4Hz,1H),7.00(d,J=7.6Hz,2H),7.10(d,J=8.4Hz,1H),7.18-7.27(m,3H),7.29-7.38(m,7H),7.41-7.44(m,2H),7.51(s,1H),7.62(d,J=8.0Hz,1H),7.74(d,J=8.4Hz,1H),7.91(t,J=8.0Hz,1H),8.13-8.15(m,2H),8.56(d,J=4.8Hz,1H)。
(2)(R,S)-M-PtLAN的合成:向带有磁力搅转子的三口烧瓶中,依次加入(R,S)-M-LAN(250mg,0.40mmol,1.0当量),二氯化铂(112mg,0.42mmol,1.05当量),然后抽换氮气三次,在氮气保护下加入苯甲腈(20mL)。随后在180℃的油浴锅中搅拌反应18小时,冷却至室温,减压蒸馏除去溶剂,得到粗品。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷的体积比为4:1-2:1,得到产物(R,S)-M-PtLAN红色固体127mg,收率39%。1H NMR(400MHz,DMSO-d6):δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J=6.8Hz,1H),6.19(d,J=7.2Hz,1H),6.26(d,J=8.0Hz,1H),6.32(d,J=8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J=7.2Hz,1H),7.08(t,J=7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J=8.8Hz,1H),7.69(d,J=8.0Hz,2H),7.99(d,J=7.6Hz,1H),8.15(d,J=8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J=5.2Hz,1H)。
实施例10:四齿环金属铂(II)配合物(R,S)-M-PtLH1的合成:
(1)配体(R,S)-LH1的合成:向带有磁力转子的干燥封管中加入ACzCzH(200mg,0.6mmol,1.0当量),2-Br(245mg,0.78mmol,1.3当量),三(二亚苄基丙酮)二钯(22mg,0.024mmol,4mol%),2-(二叔丁基膦)联苯(14mg,0.048mmol,8mol%)和叔丁醇钠(115mg,1.2mmol,2.0当量)然后抽换氮气三次,在氮气保护下加入甲苯(12mL)。该混合物在110℃的油浴锅中搅拌反应2天,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物(R,S)-LH1,白色固体214mg,收率63%。1HNMR(500MHz,DMSO-d6):δ3.21-3.24(m,1H),3.47-3.55(m,1H),5.53-5.56(m,1H),5.72(d,J=8.5Hz,1H),7.20-7.29(m,3H),7.31-7.43(m,5H),7.47-7.54(m,3H),7.57-7.59(m,2H),7.72(t,J=7.5Hz,1H),7.87-7.89(m,1H),7.95(d,J=9.0Hz,1H),8.07(t,J=2.5Hz,1H),8.30(d,J=8.5Hz,1H),8.37-8.38(m,2H),8.51(d,J=9.0Hz,1H),8.64(dd,J=8.0,1.5Hz,1H)。
(2)(R,S)-M-PtLH1的合成:向带有磁力转子的干燥三口烧瓶中依次加入配体(R,S)-LH1(212mg,0.37mmol,1.0当量),二氯化铂(104mg,0.39mmol,1.05当量)。然后抽换氮气三次,在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天,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,淋洗剂:石油醚/二氯甲烷=3:1-2:1,得到产物(R,S)-M-PtLH1,黄色固体207mg,收率74%。1H NMR(500MHz,DMSO-d6):δ3.51-3.61(m,2H),5.73-5.76(m,1H),5.98(t,J=6.0Hz,1H),6.22(d,J=7.0Hz,1H),6.72(t,J=7.5Hz,1H),7.11(t,J=7.5Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.57(t,J=7.5Hz,1H),7.63(dd,J=7.5,5.5Hz,1H),7.74-7.77(m,1H),7.85(d,J=8.5Hz,1H),8.05(d,J=8.5Hz,1H),8.18-8.20(m,1H),8.25-8.26(m,2H),8.32(d,J=8.5Hz,1H),8.54(d,J=7.5Hz,1H),9.11(dd,J=7.5,1.0Hz,1H),9.47-9.48(m,1H)。
实施例11:四齿环金属铂(II)配合物(S,R)-P-PtLH1的合成:
(1)配体(S,R)-LH1的合成:向带有磁力转子的干燥封管中加入ACzCzH(200mg,0.6mmol,1.0当量),1-Br(245mg,0.78mmol,1.3当量),三(二亚苄基丙酮)二钯(22mg,0.024mmol,4mol%),2-(二叔丁基膦)联苯(14mg,0.048mmol,8mol%)和叔丁醇钠(115mg,1.2mmol,2.0当量)然后抽换氮气三次,在氮气保护下加入甲苯(12mL)。该混合物在110℃的油浴锅中搅拌反应2天,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物(S,R)-LH1,白色固体203mg,收率60%。1HNMR(500MHz,DMSO-d6):δ3.21-3.24(m,1H),3.46-3.51(m,1H),5.52-5.55(m,1H),5.72(d,J=7.5Hz,1H),7.20-7.29(m,3H),7.31-7.42(m,5H),7.47-7.53(m,3H),7.57-7.58(m,2H),7.72(t,J=7.5Hz,1H),7.87-7.8(m,1H),7.95(d,J=8.0Hz,1H),8.07(t,J=1.5Hz,1H),8.29(d,J=7.5Hz,1H),8.36-8.38(m,2H),8.51(d,J=8.5Hz,1H),8.63(dd,J=8.0,2.0Hz,1H)。
(2)(S,R)-P-PtLH1的合成:向带有磁力转子的干燥三口烧瓶中依次加入配体(S,R)-LH1(120mg,0.21mmol,1.0当量),二氯化铂(71mg,0.27mmol,1.05当量)。然后抽换氮气三次,在氮气保护下加入苯甲腈(15mL)。该混合物在180℃的电加热套中搅拌反应3天,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,淋洗剂:石油醚/二氯甲烷=3:1-2:1,得到产物(S,R)-P-PtLH1,黄色固体83mg,收率52%。1H NMR(500MHz,DMSO-d6):δ3.51-3.61(m,2H),5.74(d,J=8.0Hz,1H),5.98(t,J=5.5Hz,1H),6.22(d,J=6.5Hz,1H),6.72(t,J=8.0Hz,1H),7.11(t,J=8.0Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.58(t,J=7.5Hz,1H),7.64(dd,J=7.5,5.5Hz,1H),7.74-7.78(m,1H),7.85(d,J=8.0Hz,1H),8.05(d,J=8.5Hz,1H),8.19(d,J=7.5Hz,1H),8.25-8.26(m,2H),8.32(d,J=8.5Hz,1H),8.54(d,J=7.5Hz,1H),9.12(dd,J=7.5,1.0Hz,1H),9.47-9.48(m,1H)。
实施例12:四齿环金属铂(II)配合物P-PtLIII-1的合成:
(1)配体LIIII-1的合成:向带有磁力转子的干燥封管中依次加入1-Br(750mg,2.39mmol,1.5当量),4-OH(400mg,1.59mmol,1.0当量),碘化亚铜(37mg,0.20mmol,10mol%),配体1(65mg,0.20mmol,10mol%)和磷酸钾(832mg,3.92mmol,2.0当量),抽换氮气三次,在氮气保护下加入二甲基亚砜(15mL)。将封管置于90℃的油浴锅中搅拌,反应2天,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,合并有机相,有机相用盐水洗涤一次,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,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到产物L III-1,白色固体431mg,收率56%。1HNMR(500MHz,DMSO-d6):δ3.22(d,J=18.5Hz,2H),3.45-3.50(m,2H),5.49-5.53(m,2H),5.69(d,J=7.5Hz,2H),7.21-7.30(m,8H),7.38(s,2H),7.42(d,J=6.5Hz,2H),7.50(t,J=8.0Hz,2H),7.65(d,J=7.5Hz,2H)。
(2)P-PtLIII-1的合成:向带有磁力转子和冷凝管的100mL干燥三口烧瓶中依次加入L6(200mg,0.41mmol,1.0当量),氯亚铂酸钾(180mg,0.43mmol,1.05当量),四正丁基溴化铵(13mg,0.041mmol,0.1当量),然后抽换氮气三次,加入预先鼓氮气的醋酸(25mL)。反应液氮气鼓泡30分钟后,室温先搅拌12小时,然后在100℃下搅拌反应2天,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,淋洗剂:石油醚/二氯甲烷=1:1,得到产物P-PtLIII-1,淡黄色固体104mg,收率36%。1H NMR(500MHz,DMSO-d6):δ3.63(d,J=18.5Hz,2H),3.67-3.72(m,2H),6.27-6.29(m,2H),6.35(d,J=7.0Hz,2H),7.27-7.33(m,6H),7.34-7.38(m,2H),7.40-7.43(m,4H),7.87(d,J=8.0Hz,2H)。
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 YvonFluoroLog-3光谱仪上进行稳态发射实验和寿命测量,或SHIMADZU RF-6000光谱仪上进行稳态发射光谱测试。低温(77K)发射光谱和寿命在用液氮冷却的2-甲基四氢呋喃(2-MeTHF)溶液中测量。Pt(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(S0)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,Pt原子使用LANL2DZ基组。
实验数据及分析:
附图1为光学纯的以金属离子为中心的螺手性四齿环金属配合物圆偏振光发光材料设计思路:光学纯原料经济易得;中心手性自主诱导螺手性的产生;圆偏振光发光材料无需手性拆分,大大节省光学纯材料的制备成本,且可以大量制备,不受手性制备色谱柱拆分的限制。
由附图2至附图5中系列不同配体结构的四齿环金属铂(II)配合物密度泛函理论(DFT)计算优化后的分子结构可知,对于含有中心手性为(R,S)的配体均可主诱导M型螺手性的产生,对于含有中心手性为(S,R)的配体均可主诱导P型螺手性的产生,且M型螺手性分子和P型螺手性分子互为对映异构体;材料分子的绝对构型得到了(R,S)-M-PtLA1的X-衍射单晶结构结构的支持(附图1左图)。此外,DFT计算优化后的四齿环金属钯(II)配合物分子结构具有相似的结果。
由附图6至附图11中所合成的光学纯螺手性材料分子在二氯甲烷溶液中室温下的发射光谱图可知,通过四齿配体结构的调控可以对环金属配合物的发光颜色近性高效的调节,可实现从约360nm的紫外区到650nm的红光区的调控;相信通过四齿配体结构的进一步调控,亦可实现红外发光。此外,由附图6至附图10中发射光谱图基本完全重合,进一步证明了附图中相应的材料分子为对映异构体。
由附图12中(S,R)-P-PtLA1和(R,S)-M-PtLA1在二氯甲烷溶液中的圆二色光谱可知,其中CD为圆二色光谱,样品浓度为5×10-5M;其谱图具有很高的镜面对称性,且在大约248、275、300和248nm具有很强的科顿效应(Cotton effect),说明对映异构体(S,R)-P-PtLA1和(R,S)-M-PtLA1对直线偏振光具有很强的偏转能力。
材料化学稳定性和热稳定性高。所设计发展的四齿配体可以和dsp2杂化的铂(II)和钯(II)金属离子很好的配位形成稳定而刚性的四边形构型分子,化学稳定性高;同时,由于所设计的中心手性配体La和另一末端配体L1或Lb之间具有较大空间位阻效应,使整个金属配合物分子可形成稳定的螺手性四齿环金属配合物,使其在溶液或高温升华过程中均不会发生消旋而丧失圆偏振发光性质。升华实验表明在320℃下分别升华出的(R,S)-M-PtLA1和(S,R)-P-PtLA1材料均未发生消旋。
由下表1中部分手性原料中间体和手性金属配合物的比旋光度数据可知,即使含有相同中心手性的原料中间体和手性金属配合物的旋光方向完全不一样,且比旋光度数值也差距巨大,说明配合物以中金属离子为中心的螺手性对整个化合物的旋光性质有着决定性的影响;此外,具有相同中心手性和螺手性的配合物,配体结构不同,比旋光度相差也会很大,如(S,R)-P-PtLA1(+477.2)和(S,R)-P-PtLA1(+784.6),说明配体结构对其旋光影响很大。同时,由于金属配合物受激发辐射发光主要涉及到金属到配体电荷转移态(MLCT)和配体内的电荷转移态(ILCT),因此金属配合物的螺手性和配体结构对其圆偏振光性质亦会有重大影响。
表1:部分手性原料中间体和手性金属配合物的比旋光度([a]20 D)
化合物或金属配合物 | 比旋光度 | 化合物或金属配合物 | 比旋光度 |
2-Br(1R,2S) | +157.2 | 1-Br(1S,2R) | -157.6 |
(R,S)-M-PtLA1 | -499.6 | (S,R)-P-PtLA1 | +477.2 |
(R,S)-M-PtLA2 | -776.2 | (S,R)-P-PtLA2 | +784.6 |
(S,R)-P-PtLC1 | +314.4 | ||
(R,S)-M-PtLAN | -457.2 | (S,R)-P-PtLAN | +439.6 |
(S,R)-P-PtLH1 | +785.6 | ||
P-PtLIII-1 | +334.8 |
注:所有样品均在二氯甲烷溶液中测定。
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13所示。在图13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。
将实施例1-12中所表示的化合物作为磷光发光材料应用于OLED器件,结构表示为:
ITO/HATCN(10nm)/TAPC(65nm)/主体材料:发光材料(10wt.%,20nm)/TmPyPB(55nm)/LiF/Al
其中,ITO为透明阳极;HATCN是空穴注入层,TAPC是空穴传输层,主体材料分别为mCBP和26mCPy,TmPyPB为电子传输层,LiF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。
器件中应用材料的分子式如下:
需要说明的是,所述结构为本发明磷光材料的一个应用的举例,不构成本发明所示磷光材料的具体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。
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)
1.一种中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料,其特征在于,其化学式如通式(I)、(I')、(II)、(II')、(III)和(III')所示,其中(I)和(I')、(II)和(II')、(III)和(III')互为对映异构体:
其中M为Pt或Pd;V1、V2、V3和V4各自独立的为N或C;
L1、L2和L3是各自独立的为五元或六元碳环、杂环、芳环或者杂芳环;La和Lb是各自独立的为五元中心手性碳环或者杂环;
A1、A2、X和X1各自独立地为O、S、CRxRy、C=O、SiRxRy、GeRxRy、NRz、PRz、RzP=O、AsRz、RzAs=O、S=O、SO2、Se、Se=O、SeO2、BH、BRz、RzBi=O或BiRz;
R1、R2和R3各自独立地表示单、双、三、四-取代或者无取代,同时R1、R2、R3、Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Rx、Ry和Rz各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的R1、R2和R3可以选择性连接形成稠环;Ra、Rb、Rc和Rd中的任意两个基团可连接形成环状体系,Re、Rf、Rg和Rh中的任意两个基团可连接形成环状体系。
2.根据权利要求1所述的具有通式(I)、(I')、(II)和(II')的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料,优选如下通式(I-A)、(I-A)、(I-B)、(I-C)、(I-D)、(I-E)、(I-F)、(I-G)、(I-H)、(I-I)、(II-A)和其对映异构体(I'-A)、(I'-A)、(I'-B)、(I'-C)、(I'-D)、(I'-E)、(I'-F)、(I'-G)、(I'-H)、(I'-I)、(II'-A):
Z和Z1各自独立地为O、S、CRxRy、C=O、SiRxRy、GeRxRy、NRz、PRz、RzP=O、AsRz、RzAs=O、S=O、SO2、Se、Se=O、SeO2、BH、BRz、RzBi=O或BiRz;
R4和R5各自独立地表示单、双、三、或四-取代或者无取代,同时R1、R2、R3、R3、R4、R5、Ra、Rb、Rc、Rd、Rx、Ry和Rz各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的R1、R2、R3、R4和R5可以选择性连接形成稠环;Ra、Rb、Rc和Rd中的任意两个基团可连接形成环状体系。
3.根据权利要求1或2所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料通式结构中的La和Lb的结构优选自:
其中Ra1、Ra2和Ra3各自独立地表示氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;
其中Rb1、Rc1和Rc2各自独立地表示单、双、三、四-取代或者无取代,同时Rb1、Rc1和Rc2各自独立地为氢、氘、卤素、烷基、环烷基、芳基、杂烷基、杂环烷基、杂芳基、卤代烷基、卤代芳基、卤代杂芳基、烷氧基、芳氧基、烯基、环烯基、炔基、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基或其组合;两个或者多个邻近的Rb1、Rc1和Rc2可以选择性连接形成稠环。
6.一种权利要求1至2中任一项所述的中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料在有机发光元件中的应用。
7.根据权利要求5所述的应用,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。
8.根据权利要求5所述的应用,其特征在于,所述发光元件包括第一电极、第二电极及设置于所述第一电极和所述第二电极之间的至少一个有机层,所述有机层包括中心手性诱导螺手性四齿环金属铂(II)和钯(II)配合物圆偏振发光材料。
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