CN115894958B - Metal main chain polymer with precise length and synthesis method and application thereof - Google Patents
Metal main chain polymer with precise length and synthesis method and application thereof Download PDFInfo
- Publication number
- CN115894958B CN115894958B CN202211633907.2A CN202211633907A CN115894958B CN 115894958 B CN115894958 B CN 115894958B CN 202211633907 A CN202211633907 A CN 202211633907A CN 115894958 B CN115894958 B CN 115894958B
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- China
- Prior art keywords
- main chain
- metal
- aminopyridine
- metal main
- polymer
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 239000005267 main chain polymer Substances 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 32
- -1 salt compound Chemical class 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 229920002521 macromolecule Polymers 0.000 claims abstract description 9
- 125000006239 protecting group Chemical group 0.000 claims abstract description 8
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000001465 metallisation Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [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 claims description 3
- BKLJUYPLUWUEOQ-UHFFFAOYSA-N 6-bromopyridin-2-amine Chemical compound NC1=CC=CC(Br)=N1 BKLJUYPLUWUEOQ-UHFFFAOYSA-N 0.000 claims description 3
- OBYJTLDIQBWBHM-UHFFFAOYSA-N 6-chloropyridin-2-amine Chemical compound NC1=CC=CC(Cl)=N1 OBYJTLDIQBWBHM-UHFFFAOYSA-N 0.000 claims description 3
- UZALKVXCOUSWSL-UHFFFAOYSA-N 6-fluoropyridin-2-amine Chemical group NC1=CC=CC(F)=N1 UZALKVXCOUSWSL-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- USVZFSNDGFNNJT-UHFFFAOYSA-N cyclopenta-1,4-dien-1-yl(diphenyl)phosphane (2,3-dichlorocyclopenta-1,4-dien-1-yl)-diphenylphosphane iron(2+) Chemical compound [Fe++].c1cc[c-](c1)P(c1ccccc1)c1ccccc1.Clc1c(cc[c-]1Cl)P(c1ccccc1)c1ccccc1 USVZFSNDGFNNJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- YGGUZZJLGAUOLQ-UHFFFAOYSA-N 6-iodopyridin-2-amine Chemical compound NC1=CC=CC(I)=N1 YGGUZZJLGAUOLQ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- WDVGNXKCFBOKDF-UHFFFAOYSA-N dicyclohexyl-[3,6-dimethoxy-2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane Chemical compound COC1=CC=C(OC)C(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1P(C1CCCCC1)C1CCCCC1 WDVGNXKCFBOKDF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims 1
- 239000003519 biomedical and dental material Substances 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 40
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 34
- 238000001228 spectrum Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002904 solvent Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000001819 mass spectrum Methods 0.000 description 19
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 18
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 238000002329 infrared spectrum Methods 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- VIRYRCBSAQHUND-UHFFFAOYSA-N n-bromopyridin-2-amine Chemical group BrNC1=CC=CC=N1 VIRYRCBSAQHUND-UHFFFAOYSA-N 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- IZWMZVDEYOKQCG-UHFFFAOYSA-N 1-(2,4-dimethoxyphenyl)-n-[(2,4-dimethoxyphenyl)methyl]methanamine Chemical compound COC1=CC(OC)=CC=C1CNCC1=CC=C(OC)C=C1OC IZWMZVDEYOKQCG-UHFFFAOYSA-N 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- JVSIBACDAOCZBA-UHFFFAOYSA-N [2-chloro-6-[2,6-di(propan-2-yl)phenyl]phenyl]-dicyclohexylphosphane Chemical group ClC=1C(=C(C=CC=1)C1=C(C=CC=C1C(C)C)C(C)C)P(C1CCCCC1)C1CCCCC1 JVSIBACDAOCZBA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical group C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002843 nonmetals Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OIASAVWSBWJWBR-UKTHLTGXSA-N trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile Chemical compound N#CC(C#N)=CC(/C)=C/C1=CC=C(C(C)(C)C)C=C1 OIASAVWSBWJWBR-UKTHLTGXSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a metal main chain macromolecule with accurate length, a synthesis method and application thereof, wherein a protected polymeric monomer is connected with a precursor compound through a coupling reaction, then deprotection is carried out to activate a functional group, and the steps are repeated for coupling end capping to obtain a ligand with accurate length; and then carrying out metallization on the ligand obtained in the steps and the metal salt compound under the heating condition to obtain the corresponding metal main chain polymer. Compared with the prior art, the metal main chain polymer synthesized by the gradual polymerization method based on the coupling reaction and the protecting group strategy has the advantages of precise and controllable length and adjustable performance, and opens up a new way for designing and synthesizing new functional polymers in the future.
Description
Technical Field
The invention relates to the technical field of polymer material synthesis, in particular to a metal main chain polymer with accurate length, and a synthesis method and application thereof.
Background
Metals and polymers are two important materials indispensable in human production and life. To meet a wide variety of application requirements, a number of effective strategies to alter their composition and structure are employed to achieve the desired performance. However, whether high concentration alloys are constructed or polymer repeat unit, chain length, stereoregularity and morphology are regulated, these modifications are generally limited to the same type of elemental metal or non-metal atom. Because of the intrinsically different electronic structures of metal and non-metal atoms, it is difficult to combine the properties of both perfectly. The construction of polymer backbones with metal atoms is a very potential strategy that allows the development of materials that have both metal and polymer advantages.
So far, due to great challenges in synthesis, the existing preparation method cannot accurately synthesize a metal main chain polymer, which is not beneficial to further research on physicochemical properties and application of the metal main chain polymer.
Disclosure of Invention
The invention aims to provide a metal main chain polymer with accurate length, and a synthesis method and application thereof.
The aim of the invention can be achieved by the following technical scheme: a method for synthesizing a metal main chain polymer with accurate length comprises the following specific synthesis steps:
(1) Connecting a protected polymerized monomer with a precursor compound through a coupling reaction, removing the protection to activate a functional group, repeating the steps, and performing coupling end capping to obtain a ligand with precise length;
(2) And (3) metallizing the ligand obtained in the step (1) and a metal salt compound under a heating condition to obtain a corresponding metal main chain polymer.
Preferably, the ligand contains one or more groups of pyridyl, naphthyridinyl, amino, hydroxyl, phenyl, sulfhydryl, carboxyl, conjugated double bond or phosphorus group;
the metal is selected from one or more of transition metals.
Further preferably, the ligand contains a pyridine or amino group.
Further preferably, when the ligand contains pyridine or amino groups, the synthesis steps are as follows:
wherein m, n is the number of repeating units, m is 0 or more, and n is 1 or more;
wherein P is n As precursor compound, D n For terminal protection intermediate, L n As a ligand, MBP is a metal main chain macromolecule;
wherein the protected polymerized monomer has the following structural general formula:
wherein X is a halogen atom, M is a metal atom, and R is an amino protecting group.
Still more preferably, the polymerized monomer protected in step (i) is an amino-protected halogenated aminopyridine chain.
Preferably, when the length of the polymerized monomer to be protected is only one pyridine, the halogenated aminopyridine is selected from 2-fluoro-6-aminopyridine, 2-bromo-6-aminopyridine, 2-chloro-6-aminopyridine, 2-iodo-6-aminopyridine, 2-bromo-4-alkyl-6-aminopyridine, 2-chloro-4-alkyl-6-aminopyridine, 2-fluoro-4-alkyl-6-aminopyridine, or 2-fluoro-4-alkyl-6-aminopyridine. Preferably 2-bromo-6-aminopyridine, 2-chloro-6-aminopyridine or 2-fluoro-6-aminopyridine.
Preferably, the amino protecting group is formyl, acetyl, t-butoxycarbonyl, benzyloxycarbonyl, benzyl, p-methoxybenzyl or 2, 4-dimethoxybenzyl.
Still more preferably, in step (i), the specific conditions for the coupling reaction are: and dissolving the protected polymerized monomer and the precursor compound in an organic solvent, and heating and coupling under the protection of nitrogen and catalysis of palladium catalyst, organophosphorus ligand and alkali to obtain the end-protected intermediate.
Still more preferably, in step (ii), the specific conditions for the deprotection reaction are: the end-protecting intermediate is dissolved in an organic solvent and deprotected under the action of an acid in an ice bath or at room temperature to activate the functional group.
Still more preferably, the number of cycles of the coupling reaction and the deprotection reaction is 1 or more.
Preferably, in the step (1), the specific step of ligand synthesis is to dissolve bromopyridine calixarene and diaminopyridine in an organic solvent, and perform heating coupling under the protection of nitrogen and under the catalysis of palladium catalyst, organophosphorus ligand and alkali to obtain a precursor compound; dissolving the protected polymerized monomer and a precursor compound in an organic solvent, and performing heating coupling under the protection of nitrogen and catalysis of a palladium catalyst, an organophosphorus ligand and a base to obtain a corresponding terminal protection intermediate; dissolving the terminal protection intermediate in an organic solvent, and removing protection under the action of acid in ice bath or at room temperature to activate the functional group; after a certain number of iterations, the precursor compound with the re-activated functional group and the end-capping monomer are dissolved in an organic solvent, and the corresponding ligand is obtained through heating and coupling under the protection of nitrogen and the catalysis of palladium catalyst, organophosphorus ligand and alkali.
Further preferably, the calixarene is selected from calix [4] arene, 4-alkylcalix [4] arene or 4-sulfonylcalix [4] arene, preferably t-butylcalix [4] arene.
Preferably, the organic solvent is selected from toluene, pyridine, picoline, 1, 4-dioxane, dichloromethane, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone or xylene, preferably 1, 4-dioxane, toluene, pyridine or 4-picoline.
Preferably, the palladium catalyst is selected from tris (dibenzylideneacetone) dipalladium, palladium acetate, (2-dicyclohexylphosphine-3, 6-dimethoxy-2 ',4',6' -triisopropyl-1, 1' -biphenyl) [2- (2-aminoethylphenyl) ] palladium chloride, chloro (2-dicyclohexylphosphino-2 ',6' -diisopropyl-1, 1' -biphenyl) [2- (2-aminoethylphenyl) ] palladium (II) or dichloro [1,1' -bis (diphenylphosphino) ferrocene ] palladium, preferably tris (dibenzylideneacetone) dipalladium, palladium acetate or dichloro [1,1' -bis (diphenylphosphino) ferrocene ] palladium.
Preferably, the organophosphorus ligand is selected from 1, 3-bis (diphenylphosphorus) propane, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropylbiphenyl or dicyclohexyl [3, 6-dimethoxy-2', 4',6' -triisopropyl [1,1 '-biphenyl ] -2-yl ] phosphine, preferably 1, 3-bis (diphenylphosphorus) propane, 1' -binaphthyl-2, 2 '-bisdiphenylphosphine or 2-dicyclohexylphosphine-2', 4',6' -triisopropylbiphenyl.
Preferably, the base is selected from potassium tert-butoxide, cesium carbonate, sodium tert-butoxide, diisopropylethylamine, sodium carbonate or potassium carbonate, preferably potassium tert-butoxide or cesium carbonate.
Preferably, the acid is selected from glacial acetic acid, hydrochloric acid, hydrobromic acid or trifluoroacetic acid.
Still more preferably, the specific conditions for the end-capping reaction of step (iii) are: and (3) dissolving the end-capping monomer and the precursor compound in an organic solvent, and heating and coupling under the protection of nitrogen and catalysis of a palladium catalyst, an organophosphorus ligand and a base to obtain the ligand.
Preferably, the end-capping monomer in step (iii) has the following structural formula:
wherein n is 0 or more, and X is one of halogen atoms such as fluorine, chlorine, bromine, iodine and the like.
Still more preferably, the specific conditions for the metal-complexing reaction of step (iv) are: and dissolving the ligand and the metal salt compound in an organic solvent, and heating under the protection of nitrogen to carry out metallization to obtain the metal main chain polymer.
Preferably, the metal salt compound is selected from the group consisting of acetate, chloride, bromide, sulfate or trifluoroacetate salts of alkali metals.
The metal main chain macromolecule with accurate length is prepared by adopting the synthesis method.
The application of a metal main chain macromolecule with precise length is that the macromolecule is applied to photoelectric materials, superconducting materials or biomedical materials.
Aiming at the problem that the prior art cannot accurately synthesize a polymer with metal as a main chain, the invention provides a method for synthesizing a metal main chain polymer with accurate length.
Compared with the prior art, the invention has the following advantages:
1. the invention creatively provides a novel preparation method of a metal main chain polymer, which can accurately synthesize the metal main chain polymer through a coupling reaction and a gradual polymerization method of a protecting group strategy;
2. the invention can obtain metal main chain polymers with different lengths by regulating and controlling the length of the protected polymerized monomer, the reaction iteration times and the length of the end-capped monomer, and the method is simple, convenient and efficient, thereby opening up a new way for designing and synthesizing new functional polymers in the future.
Drawings
FIG. 1 is a matrix assisted laser Desorption ionization time of flight mass spectrum (MALDI-TOF MS) of a metal backbone polymer according to the present invention;
FIG. 2 is a graph showing the ultraviolet-visible absorption spectrum of a metal main chain polymer in the present invention;
FIG. 3 is a graph of HOMO and LUMO levels of a metal backbone polymer according to the present invention;
FIG. 4 is an enlarged view of matrix assisted laser Desorption ionization time of flight mass spectrometry (MALDI-TOF MS) of a metal backbone polymer having a length of 21 nickel atoms according to the present invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
In the following examples:
the bromocalixarene was synthesized by the method described in the literature (Chin. J Polym. Sci.2022,41,1-4.).
The bromoaminopyridine chain was synthesized by the method described in the literature (Tetrahedron Lett.2004,45, 7765-7769.).
Example 1
A method for synthesizing a metal main chain polymer with accurate length comprises the following specific steps:
(1) Synthesis of ligands
a. Synthesis of precursor compounds
Bromopyridine calixarene (1.0 g,0.079 mmol) and 2, 6-diaminopyridine (1.72 g,0.016 mol) were dissolved in xylene (20 mL). Tridibenzylideneacetone dipalladium (72.00 mg,0.079 mmol), 1, 3-bis (diphenylphosphorus) propane (65.00 mg,0.157 mmol) and potassium tert-butoxide (706 mg,6.29 mmol) were added rapidly under nitrogen and then reacted under reflux for 2h. After the solution is cooled, pouring the reaction solution into petroleum ether, filtering and washing a filter cake with deionized water, dissolving and filtering the filter cake with tetrahydrofuran to remove insoluble impurities, and distilling under reduced pressure to remove the solvent to obtain brown solid powder P 1 1.02g, yield 95%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ8.80(s,4H),7.55(t,J＝7.9Hz,4H),7.14(s,8H),6.94(t,J＝8.0Hz,4H),6.78(d,J＝7.9Hz,4H),6.73(d,J＝8.0Hz,4H),6.64(d,J＝8.0Hz,4H),5.87(d,J＝7.8Hz,4H),5.43(s,8H),3.98(d,J＝12.5Hz,4H),3.11(d,J＝12.7Hz,4H),1.18(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.5,158.4,153.5,152.6,147.3,146.1,139.8,138.6,134.8,125.3,104.3,101.5,100.4,99.6,34.3,31.7,31.5。
FTIR(KBr,cm -1 ):3487,3197,3122,3055,2960,2925,2865,1611,1574,1520,1448,1436,1395,1361,1317,1277,1249,1215,1191,1152,1120,1079,1032,870,784,726。
the high resolution mass spectrum data are as follows: theoretical value of high resolution mass spectrum C 84 H 88 N 16 O 4 [M+H] + 1385.7247; found 1385.7259.
Synthesis of 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer
2, 6-dibromopyridine (11.0 g,0.046 mol) and bis (2, 4-dimethoxybenzyl) amine (10.0 g,0.032 mol) were dispersed in xylene (70 mL). N, N-diisopropylethylamine (16 mL,0.092 mol) was slowly added under nitrogen, followed by reflux for 24h. After the reaction was completed, the solvent was distilled off under reduced pressure, and purified by column chromatography (ethyl acetate: petroleum ether=1:8) to give 14.3g of a white solid powder, with a yield of 96%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,CDCl 3 ,ppm):δ7.16–7.09(m,3H),6.66(d,J＝7.5Hz,1H),6.46(d,J＝2.4Hz,2H),6.42(dd,J＝8.3,2.4Hz,2H),6.25(d,J＝8.4Hz,1H),4.71(s,4H),3.81(s,6H),3.78(s,6H)。
13 C NMR(100MHz,CDCl 3 ,ppm):δ159.9,158.7,158.4,139.9,139.1,128.8,118.3,114.3,104.4,103.7,98.4,55.4,55.2,46.5。
FTIR(KBr,cm -1 ):3108,3099,3074,3012,2989,2963,2940,2909,2880,2831,1618,1588,1539,1505,1491,1464,1451,1435,1423,1414,1374,1363,1307,1280,1254,1210,1175,1166,1155,1110,1081,1065,1038,997,958,920,832,821,784,775,726,718,669,658,631,580,524,516,502,458。
the high resolution mass spectrum data are as follows: high resolutionSpectral theory C 23 H 24 BrN 2 O 4 [M+H] + 473.1070; found 473.1060.
c. Synthesis of ligands
(1) To the precursor compound P 1 (1.00 g,0.72 mmol) and 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer (5.60 g,0.012 mol) were dissolved in ultra-dry 1, 4-dioxane (40 mL). Tridibenzylideneacetone dipalladium (265 mg,0.29 mmol), 1, 3-bis (diphenylphosphorus) propane (238 mg,0.58 mmol) and potassium tert-butoxide (649 mg,5.76 mmol) were added rapidly under nitrogen, followed by reflux for 2h. After the reaction, the solvent is removed by distillation under reduced pressure, the mixture is washed with petroleum ether and filtered, a filter cake is dissolved by methylene dichloride, insoluble impurities are removed by filtration, and the solvent is removed by distillation under reduced pressure to obtain a white solid powder product D 2 2.08g, yield 98%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ8.90(s,4H),8.65(s,4H),7.60(t,J＝7.8Hz,4H),7.28(t,J＝8.0Hz,4H),7.14(s,8H),6.95–6.90(m,20H),6.84(t,J＝7.9Hz,12H),6.55(d,J＝2.3Hz,8H),6.43(dd,J＝8.4,2.4Hz,8H),5.91(d,J＝8.2Hz,4H),4.57(s,16H),3.99(d,J＝12.4Hz,4H),3.76(s,24H),3.71(s,24H),3.13(d,J＝12.7Hz,4H),1.18(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.5,159.9,158.4,157.5,153.4,153.3,153.0,152.1,147.3,146.2,140.1,139.2,138.4,134.8,127.9,125.4,118.5,104.7,103.9,103.1,102.0,99.5,98.8,97.3,55.7,55.6,46.2,34.3,31.7,31.4。
FT-IR(KBr,cm -1 ):3195,3124,3048,2996,2954,2934,2866,2834,1607,1590,1569,1505,1434,1362,1321,1285,1244,1208,1191,1155,1119,1038,976,958,934,921,870,831,824,776,722,635,615,596,577,553,515,456,418。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 176 H 184 N 24 O 20 :[M+Na] + 2976.4009; found 2976.7283.
(2) Intermediate D will be protected 2 (2.01 g,0.68 mmol) was dissolved in dichloromethane (30 mL), glacial acetic acid (4 mL,0.068 mol) was added under nitrogen and the reaction stirred in an ice-water bath for 1h. After the completion of the reaction, the solvent was distilled off under reduced pressure, dissolved in methanol (30 mL), filtered, and an aqueous sodium hydrogencarbonate solution (20 mL) was added to the filtrate, filtered, washed with deionized water (100 mL), and dried to give a brown powder solid product P 2 1.16g, 97% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ8.95(s,4H),8.60(s,4H),7.63(t,J＝7.9Hz,4H),7.23(t,J＝7.9Hz,4H),7.17(s,8H),7.09(d,J＝7.9Hz,8H),6.94(d,J＝7.9Hz,4H),6.89(d,J＝8.1Hz,4H),6.85(t,J＝8.3Hz,8H),5.94(d,J＝7.8Hz,4H),5.56(s,8H),4.01(d,J＝12.4Hz,4H),3.16(d,J＝12.8Hz,4H),1.20(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.5,158.6,153.5,153.4,153.3,152.1,147.3,146.2,140.1,138.9,138.5,134.8,125.4,104.5,104.0,102.8,101.9,99.9,99.5,34.3,31.8,31.4。
FT-IR(KBr,cm -1 ):3464,3197,3112,3054,2961,2904,2866,1684,1608,1575,1508,1437,1361,1284,1235,1208,1191,1153,1082,1057,1037,868,849,802,782,725,651,598。
the high resolution mass spectrum data are as follows: theoretical value of high resolution mass spectrum C 104 H 104 N 24 O 4 :[M+H] + 1753.8745; found 1753.8745.
(3) To the precursor compound P 2 (1.26 g,0.72 mmol) and 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer (5.60 g,0.012 mol) were dissolved in ultra-dry 1, 4-dioxane (40 mL). Palladium acetate (130 mg,0.58 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (361 mg,0.58 mmol) and cesium carbonate (1.9 g,5.76 mmol) were added rapidly under nitrogen, followed by a reflux reaction for 2h. After the reaction, the solvent was distilled off under reduced pressure, washed with petroleum ether, filtered, and the cake was dissolved in methylene chloride and filtered to remove impuritiesDissolving impurities, distilling under reduced pressure to remove solvent to obtain white solid powder product D 3 2.34g, 98% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ8.98(s,4H),8.77(s,4H),8.74(s,4H),7.63(t,J＝7.9Hz,4H),7.30–7.22(m,12H),7.20–7.13(m,16H),7.06(d,J＝7.6Hz,4H),7.01(d,J＝7.7Hz,4H),6.94(d,J＝8.4Hz,12H),6.84(d,J＝7.6Hz,8H),6.57(d,J＝2.3Hz,8H),6.44(dd,J＝8.4,2.3Hz,8H),5.94(d,J＝8.2Hz,4H),4.60(s,16H),4.02(d,J＝9.5Hz,4H),3.78(s,24H),3.72(s,24H),3.17(d,J＝11.5Hz,4H),1.20(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,159.9,158.4,157.4,153.4,153.3,153.1,153.0,153.0,152.1,147.3,146.2,140.1,139.1,138.7,134.8,130.8,130.7,129.2,129.1,128.2,127.8,125.4,118.5,104.8,104.2,103.3,102.0,99.5,98.8,97.2,55.8,55.6,46.5,34.3,31.8,31.5。
FT-IR(KBr,cm -1 ):3197,3132,3055,3029,2995,2954,2934,2865,2834,1607,1589,1575,1539,1506,1430,1362,1287,1246,1208,1191,1155,1119,1037,976,933,870,781,723,700,516,457,419。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 196 H 200 N 32 O 20 :[M+Na] + 3344.5508; found 3344.9637.
(4) Intermediate D will be protected 3 (2.26 g,0.68 mmol) was dissolved in dichloromethane (30 mL), trifluoroacetic acid (5 mL,0.068 mol) was added under nitrogen and the reaction stirred in an ice-water bath for 1h. After the completion of the reaction, the solvent was distilled off under reduced pressure, dissolved in methanol (30 mL), filtered, and an aqueous sodium hydrogencarbonate solution (20 mL) was added to the filtrate, filtered, washed with deionized water (100 mL), and dried to give a brown powder solid product P 3 1.40g, 97% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.02(s,4H),8.81(s,4H),8.75(s,4H),7.66(t,J＝7.9Hz,4H),7.43(t,J＝8.0Hz,4H),7.33(d,J＝7.9Hz,4H),7.25(d,J＝7.9Hz,4H),7.23–7.20(m,8H),7.17(d,J＝7.9Hz,4H),7.13(d,J＝7.9Hz,4H),7.05(d,J＝7.9Hz,4H),7.00(d,J＝7.9Hz,4H),6.97(d,J＝7.8Hz,4H),6.90(d,J＝7.7Hz,4H),6.86(d,J＝8.0Hz,4H),5.97(d,J＝7.8Hz,4H),5.61(s,8H),4.05(d,J＝12.2Hz,4H),3.20(d,J＝13.0Hz,4H),1.23(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,158.7,153.6,153.4,153.0,152.9,152.2,147.4,146.3,140.1,138.9,138.8,134.8,125.4,104.5,104.3,103.6,103.2,103.0,102.0,99.8,99.7,34.4,31.8,31.4。
FT-IR(KBr,cm -1 ):3480,3196,3125,355,3029,3002,2958,2912,2865,2836,1605,1575,1506,1431,1361,1290,1247,1207,1190,1154,1119,1035,871,782,724,700,551,513。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 124 H 120 N 32 O 4 :[M+Na] + 2144.0063; found 2144.1116.
(5) To the precursor compound P 3 (318 mg,0.15 mmol) and 2-chloropyridine (204 mg,1.8 mmol) were dissolved in ultra-dry tetrahydrofuran (20 mL), and palladium acetate (7 mg,0.030 mmol), 1, 3-bis (diphenylphosphorus) propane (12 mg,0.030 mmol) and potassium tert-butoxide (135 mg,1.2 mmol) were added rapidly under nitrogen and reacted under reflux for 12h. Removing solvent by reduced pressure distillation after the reaction is finished, washing with petroleum ether, filtering, washing filter cake with deionized water, dissolving with tetrahydrofuran, filtering to remove insoluble impurities, and removing solvent by reduced pressure distillation to obtain brown solid powder product L 4 321mg, 88% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.35(s,4H),9.03(s,8H),8.88(s,4H),8.21(dd,J＝5.3,2.0Hz,4H),7.96(d,J＝8.4Hz,4H),7.66–7.60(m,8H),7.52–7.46(m,12H),7.42(d,J＝7.9Hz,4H),7.36(d,J＝8.0Hz,4H),7.22–7.16(m,12H),7.11(d,J＝7.7Hz,4H),7.07(d,J＝7.9Hz,4H),7.02(d,J＝7.8Hz,4H),6.98(d,J＝7.9Hz,4H),6.87–6.82(m,8H),4.05(d,J＝11.7Hz,4H),3.20(d,J＝11.8Hz,4H),1.22(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,154.9,153.4,153.1,153.0,152.2,147.9,147.4,146.3,140.3,140.1,139.1,138.8,137.8,134.8,132.1,130.8,130.7,129.2,129.1,128.8,128.8,125.5,116.1,112.4,104.6,104.3,103.7,103.5,101.9,34.4,31.8,31.5。
FT-IR(KBr,cm -1 ):3273,3195,3107,3054,3029,2959,2930,2865,1601,1574,1507,1480,1428,1361,1305,1246,1190,1152,1120,1103,1072,1050,1029,988,949,870,779,725,700,666,614,593,553,513,448,418。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 144 H 132 N 36 O 4 :[M+Na] + 2452.1123; found 2452.3661.
(2) Synthesis of Metal backbone Polymer
Ligand L 4 (36 mg,0.015 mmol), anhydrous nickel chloride (26 mg,0.20 mmol) and naphthalene (30 g) were mixed and reacted under nitrogen with stirring at 200℃for 24h. After cooling to 80 ℃, petroleum ether is added for filtration to remove naphthalene, and dichloromethane is used for washing a filter cake, and the obtained filtrate is used for removing solvent to obtain 25mg of ferrous metal main chain polymer solid powder with the yield of 55%.
The infrared spectrogram data are as follows:
FTIR(KBr,cm -1 ):3055,3029,2955,2926,2857,1599,1583,1558,1544,1419,1361,1336,1307,1279,1256,1233,1194,1155,1126,1014,968,948,906,871,770,726,703,654,434,418。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 144 H 116 ClN 36 Ni 9 O 4 [M+H] + 2978.3833; found 2978.1902.
Example 2
A method for synthesizing a metal main chain polymer with accurate length comprises the following specific steps:
(1) Synthesis of ligands
a. Synthesis of precursor compounds
Preparation process and example 1 step (1) c. (4) precursor compound P 3 The synthesis method is the same.
Synthesis of 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer
The preparation process is the same as the synthesis method of the b.2, 4-dimethoxybenzyl-protected monopyridine polymer monomer in step (1) of example 1.
c. Synthesis of ligands
(1) To the precursor compound P 3 (1.53 g,0.72 mmol) and 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer (5.60 g,0.012 mol) were dissolved in ultra-dry 1, 4-dioxane (40 mL). Tridibenzylideneacetone dipalladium (265 mg,0.29 mmol), 1, 3-bis (diphenylphosphorus) propane (238 mg,0.58 mmol) and potassium tert-butoxide (649 mg,5.76 mmol) were added rapidly under nitrogen, followed by reflux for 2h. After the reaction, the solvent is removed by distillation under reduced pressure, the mixture is washed with petroleum ether and filtered, a filter cake is dissolved by methylene dichloride, insoluble impurities are removed by filtration, and the solvent is removed by distillation under reduced pressure to obtain a white solid powder product D 4 2.60g, yield 98%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.01(s,4H),8.89(s,4H),8.82(s,8H),7.47(t,J＝7.8Hz,8H),7.37(d,J＝8.3Hz,4H),7.30(t,J＝8.0Hz,8H),7.27–7.23(m,8H),7.20–7.14(m,16H),7.08(d,J＝7.7Hz,8H),6.95(d,J＝8.5Hz,16H),6.82(d,J＝7.6Hz,4H),6.58(d,J＝2.3Hz,8H),6.45(dd,J＝8.4,2.4Hz,8H),5.95(d,J＝8.3Hz,4H),4.62(s,16H),4.03(d,J＝8.3Hz,4H),3.78(s,24H),3.72(s,24H),3.18(d,J＝8.2Hz,4H),1.21(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,162.8,159.9,158.4,157.4,156.0,153.4,153.1,152.2,146.3,140.2,139.1,138.6,134.8,129.4,128.7,127.9,125.8,125.5,118.5,104.7,103.5,103.3,99.5,98.8,97.1,55.7,55.6,46.5,34.3,31.8,31.3。
FT-IR(KBr,cm -1 ):3195,3117,3095,3053,3026,2997,2955,2936,2913,2867,2834,1606,1590,1574,1506,1427,1362,1287,1247,1208,1191,1155,1119,1039,977,934,870,829,780,724,667,599,512,457,419。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 216 H 216 N 40 O 20 :[M+Na] + 3712.7004; found 3712.5855.
(2) Intermediate D will be protected 4 (2.51 g,0.68 mmol) was dissolved in dichloromethane (30 mL), glacial acetic acid (4 mL,0.068 mol) was added under nitrogen and the reaction stirred in an ice-water bath for 1h. After the completion of the reaction, the solvent was distilled off under reduced pressure, dissolved in methanol (30 mL), filtered, and an aqueous sodium hydrogencarbonate solution (20 mL) was added to the filtrate, filtered, washed with deionized water (100 mL), and dried to give a brown powder solid product P 4 1.64g, 97% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.02(s,4H),8.92(s,4H),8.84(s,4H),8.76(s,4H),7.65(t,J＝7.6Hz,4H),7.49(d,J＝7.9Hz,4H),7.45(d,J＝4.9Hz,4H),7.43–7.38(m,8H),7.26(t,J＝7.9Hz,12H),7.22–7.16(m,16H),7.03(d,J＝7.9Hz,4H),6.98(d,J＝8.0Hz,8H),6.88–6.84(m,4H),5.97(d,J＝8.0Hz,4H),5.61(s,8H),4.04(d,J＝11.1Hz,4H),3.19(d,J＝11.2Hz,4H),1.22(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,158.7,153.6,153.4,153.2,153.0,152.2,147.3,146.3,140.1,139.1,138.9,134.8,125.4,104.5,104.2,103.8,103.5,103.4,103.3,103.2,102.0,99.6,34.4,31.8,31.3。
FT-IR(KBr,cm -1 ):3481,3196,3121,3055,3030,2959,2903,2865,1604,1574,1515,1429,1361,1289,1248,1191,1154,1120,1027,987,871,781,725,701,549,447。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 144 H 136 N 40 O 4 :[M+Na] + 2512.1558; found 2512.2711.
(3) To the precursor compound P 4 (1.79 g,0.72 mmol) and 2, 4-dimethoxybenzyl-protected monopyridine polymerized monomer (5.60 g,0.012 mol) were dissolved in ultra-dry 1, 4-dioxane (40 mL). Palladium acetate (130 mg,0.58 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (361 mg,0.58 mmol) and cesium carbonate (1.9 g,5.76 mmol) were added rapidly under nitrogen, followed by a reflux reaction for 2h. After the reaction, the solvent is removed by distillation under reduced pressure, the mixture is washed with petroleum ether and filtered, a filter cake is dissolved by methylene dichloride, insoluble impurities are removed by filtration, and the solvent is removed by distillation under reduced pressure to obtain a white solid powder product D 5 2.86g, 98% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.03(s,4H),8.95(s,4H),8.92(s,4H),8.85(s,4H),8.82(s,4H),7.67(t,J＝7.9Hz,4H),7.49–7.45(m,8H),7.39(d,J＝8.6Hz,4H),7.29(dd,J＝8.0,4.4Hz,12H),7.22–7.18(m,16H),7.15(d,J＝7.9Hz,8H),7.06(dd,J＝10.8,7.8Hz,8H),6.95(d,J＝8.3Hz,12H),6.88(dd,J＝12.8,8.0Hz,8H),6.82(d,J＝7.8Hz,4H),6.58(d,J＝2.2Hz,8H),6.45(dd,J＝8.4,2.4Hz,8H),5.96(d,J＝8.4Hz,4H),4.62(s,16H),4.05(d,J＝9.2Hz,4H),3.79(s,24H),3.73(s,24H),3.20(d,J＝9.3Hz,4H),1.22(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,159.9,158.4,157.5,153.4,153.1,153.1,153.1,152.2,147.4,146.3,140.2,139.1,138.7,134.8,127.9,125.5,118.5,104.8,104.3,103.6,103.5,103.3,102.0,99.5,98.8,97.2,55.8,55.6,46.5,34.4,31.8,31.6。
FT-IR(KBr,cm -1 ):3197,3123,3056,2996,2955,2934,3908,2866,2835,1606,1589,1575,1540,1506,1426,1363,1288,1248,1207,1190,1154,1122,1038,977,935,871,824,778,722,668,596,517,457,419。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 236 H 232 N 48 O 20 :[M+Na] + 4080.8503; found 4081.0104.
(4) Will protect the middleBody D 5 (2.60 g,0.68 mmol) was dissolved in dichloromethane (30 mL), trifluoroacetic acid (5 mL,0.068 mol) was added under nitrogen and the reaction stirred in an ice-water bath for 1h. After the completion of the reaction, the solvent was distilled off under reduced pressure, dissolved in methanol (30 mL), filtered, and an aqueous sodium hydrogencarbonate solution (20 mL) was added to the filtrate, filtered, washed with deionized water (100 mL), and dried to give a brown powder solid product P 5 1.89g, 97% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.05(s,4H),8.99(s,8H),8.87(s,4H),8.79(s,4H),7.71–7.63(m,4H),7.53–7.39(m,20H),7.30–7.20(m,32H),7.05–6.87(m,20H),5.99(d,J＝8.3Hz,4H),5.63(s,8H),4.06(d,J＝8.9Hz,4H),3.21(d,J＝8.7Hz,4H),1.23(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,158.7,153.6,153.4,153.2,153.1,152.2,147.4,146.3,140.1,139.0,134.8,125.5,104.2,103.7,103.5,103.3,102.1,99.8,99.7,34.4,31.8,31.6。
FT-IR(KBr,cm -1 ):3481,3195,3122,3054,2953,2901,2864,1604,1273,1507,1423,1361,1290,1246,1190,1151,1119,1081,985,870,776,722,665,594,550,445。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 164 H 152 N 48 O 4 :[M+Na] + 2880.3057; found 2880.5253.
(5) To the precursor compound P 5 (428 mg,0.15 mmol) and 2-bromopyridine (284 mg,1.8 mmol) were dissolved in toluene (20 mL), and palladium acetate (7 mg,0.030 mmol), 1, 3-bis (diphenylphosphorus) propane (12 mg,0.030 mmol) and cesium carbonate (399mg, 1.2 mmol) were added rapidly under nitrogen and reacted under reflux for 12h. Removing solvent by reduced pressure distillation after the reaction is finished, washing with petroleum ether, filtering, washing filter cake with deionized water, dissolving with tetrahydrofuran, filtering to remove insoluble impurities, and removing solvent by reduced pressure distillation to obtain brown solid powder product L 6 403mg, 85% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.37(s,8H),9.06(d,J＝12.9Hz,16H),8.21(s,8H),7.95(d,J＝8.2Hz,8H),7.64(s,12H),7.51(s,16H),7.36–7.30(m,16H),7.23–7.18(m,16H),7.12–7.08(m,8H),6.85(s,12H),4.04(d,J＝8.1Hz,4H),3.21(d,J＝8.1Hz,4H),1.22(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.5,154.8,153.1,152.2,147.9,146.3,142.0,139.2,137.9,134.8,125.4,116.2,112.4,107.2,103.7,34.3,31.7,31.5。
FT-IR(KBr,cm -1 ):3267,3195,3105,3050,3025,2959,2928,2903,2865,1601,1574,1506,1421,1302,1247,1190,1151,1120,1079,987,880,868,849,777,723,655,594,447。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 484 H 164 N 52 O 4 :[M+Na] + 3188.4119; found 3188.3825.
(2) Synthesis of Metal backbone Polymer
Ligand L to be synthesized 6 (48 mg,0.015 mmol), nickel acetate tetrahydrate (73 mg,0.29 mmol) and naphthalene (40 g) were mixed and reacted under nitrogen with stirring at 200℃for 24h. After cooling to 80 ℃, petroleum ether is added for filtration to remove naphthalene, and dichloromethane is used for washing a filter cake, and the obtained filtrate is used for removing solvent to obtain 12mg of ferrous metal main chain polymer solid powder with 20% yield.
The infrared spectrogram data are as follows:
FTIR(KBr,cm -1 ):2955,2925,2855,1600,1553,1545,1425,1353,1343,1305,1277,1258,1193,1155,1125,1061,1011,845,774,723,704。
the mass spectrum data are as follows:
theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 184 H 140 ClN 52 Ni 13 O 4 [M+H] + 3942.3564; found 3942.0812.
Example 3
A method for synthesizing a metal main chain polymer with accurate length comprises the following specific steps:
(1) Synthesis of ligands
a. Synthesis of precursor compounds
Preparation process and example 2 step (1) c. (4) precursor compound P 5 The synthesis method is the same.
b. Synthesis of ligands
To the precursor compound P 5 (200 mg,0.070 mmol) and the bromoaminopyridine chain (133 mg, 0.850 mmol) were dissolved in pyridine (20 mL). Tridibenzylideneacetone dipalladium (7.1 mg,0.008 mmol), 1, 3-bis (diphenylphosphorus) propane (6.5 mg,0.016 mmol) and potassium tert-butoxide (62.8 mg,0.560 mmol) were added rapidly under nitrogen, followed by reflux reaction for 24h. After the reaction is finished, the reaction solution is poured into ice water, filtered, and then the filter cake is washed by tetrahydrofuran, and the brown gray product L is obtained after drying 10 198mg, 89% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the infrared spectrum data are as follows:
1 H NMR(400MHz,DMSO-d 6 ,ppm):δ9.36(s,4H),9.06(s,36H),8.22(s,4H),7.92(s,4H),7.66(s,12H),7.55–7.50(m,32H),7.29(d,J＝7.8Hz,48H),7.21(d,J＝6.7Hz,16H),7.10–7.06(m,8H),6.98(d,J＝6.0Hz,8H),6.91–6.85(m,12H),4.05(d,J＝13.1Hz,4H),3.19(d,J＝13.1Hz,4H),1.22(s,36H)。
13 C NMR(100MHz,DMSO-d 6 ,ppm):δ163.6,155.0,153.1,152.2,147.3,146.3,139.2,138.0,134.8,129.1,125.4,119.1,116.1,112.5,103.7,34.4,31.8,31.4。
FT-IR(KBr,cm -1 ):3276,3192,3122,3048,3028,2954,2928,2905,2863,1602,1573,1509,1429,1295,1247,1190,1150,987,870,777,723,448。
the mass spectrum data are as follows: theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 264 H 228 N 84 O 4 [M+Na] + :4644.1260; found 4644.5219.
(2) Synthesis of Metal backbone Polymer
Ligand L to be synthesized 10 (20 mg,0.005 mmol) and nickel acetate tetrahydrate (33.8 mg,0.136 mmol) were dissolved in anhydrous dimethyl sulfoxide (20 mL) and reacted under nitrogen protection at 200℃for 12h with stirring. After the reaction was completed, the solvent was distilled off under reduced pressure, and then dissolved and filtered with methylene chloride, whereby 2mg of a polymer solid powder having a black metal main chain was obtained in 8% yield.
The infrared spectrogram data are as follows:
FTIR(KBr,cm -1 ):2957,2923,2853,1643,1617,1558,1548,1540,1522,1514,1454,1426,1383,1314,1262,1197,1155,1098,1027,876,803,665,636,598,560,509,501,465,424,405。
the mass spectrum data are as follows: theoretical value of Mass Spectrometry (MALDI-TOF, m/z) C 264 H 188 ClN 84 Ni 21 O 4 [M+H] + 5870.3324; found 5869.7637.
The test results show that a series of metal main chain macromolecules with precise lengths are prepared by the gradual polymerization method based on the coupling reaction and the protecting group strategy, and the highest molecular weight can reach more than 5800 (figure 1 and example 3). Its maximum absorption wavelength visible in dichloromethane is in the wavelength range of 350-430nm and gradually red-shifts with increasing metal chain length (fig. 2). At the same time, as the length of the metal chain increases, its HOMO level gradually increases and then remains substantially constant, while the LUMO level remains substantially constant, and correspondingly, the band gap gradually decreases and finally remains substantially constant (fig. 3).
The nuclear magnetic data are obtained by testing with a Bruker AVANCE III HD M nuclear magnetic resonance spectrometer, and deuterated chloroform or deuterated dimethyl sulfoxide is used as a solvent; the molecular weight is tested by using a Bruker McRIOTOF11 high-resolution mass spectrometer and an AB SCIEX 5800 matrix-assisted laser desorption ionization time-of-flight mass spectrometer, trans-2- [3- (4-tert-butylphenyl) -2-methyl-2-propenylidene ] malononitrile is used as a matrix, and sodium trifluoroacetate is used as a sodium salt; the infrared signal is obtained by using a Thermofisher Nicolet 6700 infrared spectrometer to test, and the potassium bromide powder is used as a diluent to carry out tabletting and sample preparation; the UV-visible absorption spectrum was measured using a Perkin-Elmer Lambda 750 UV-visible spectrophotometer; the energy level and the band gap are calculated according to the cyclic voltammetry test result.
The invention carries out gradual polymerization based on the coupling reaction and the protecting group strategy, and the obtained metal main chain polymer has the advantages of precise and controllable length and adjustable performance, thereby opening up a new way for the design and synthesis of new functional polymers in the future.
The metal main chain macromolecule synthesized by the invention shows a certain regular change in the optical and electrical properties along with the increase of the length of the metal chain, and is expected to be widely applied to photoelectric, superconducting and biomedical materials.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. The synthesis method of the metal main chain polymer with the precise length is characterized by comprising the following specific synthesis steps of:
(1) Connecting a protected polymerized monomer with a precursor compound through a coupling reaction, removing the protection to activate a functional group, repeating the steps, and performing coupling end capping to obtain a ligand with precise length;
(2) Carrying out metallization on the ligand obtained in the step (1) and a metal salt compound under a heating condition to obtain a corresponding metal main chain polymer;
the metal is selected from one of transition metals;
the synthesis steps of the metal main chain macromolecule are as follows:
；
wherein m, n is the number of repeating units, m is 0 or more, and n is 1 or more;
wherein i is the cycle times of the coupling reaction and the deprotection reaction, i is more than or equal to 1, and ni=m+n+1 during coupling and ni=n during deprotection in the same cycle;
wherein P is n As precursor compound, D ni For terminal protection intermediate, L n As a ligand, MBP is a metal main chain macromolecule;
wherein the protected polymerized monomer has the following structural general formula:
；
wherein X is a halogen atom and R is an amino protecting group.
2. The method of claim 1, wherein the polymer monomer protected in step (i) is an amino-protected halogenated aminopyridine chain;
when the length of the polymerized monomer to be protected is only one pyridine, the halogenated aminopyridine is selected from 2-fluoro-6-aminopyridine, 2-bromo-6-aminopyridine, 2-chloro-6-aminopyridine, 2-iodo-6-aminopyridine, 2-bromo-4-alkyl-6-aminopyridine, 2-chloro-4-alkyl-6-aminopyridine, or 2-fluoro-4-alkyl-6-aminopyridine;
the amino protecting group is formyl, acetyl, t-butoxycarbonyl, benzyloxycarbonyl, benzyl, p-methoxybenzyl or 2, 4-dimethoxybenzyl.
3. The method for synthesizing a metal-backbone polymer having a precise length according to claim 1, wherein in the step (i), the specific conditions of the coupling reaction are: dissolving a protected polymerized monomer and a precursor compound in an organic solvent, and heating and coupling under the protection of nitrogen and catalysis of a palladium catalyst, an organophosphorus ligand and a base to obtain a terminal protection intermediate;
in step (ii), the specific conditions for the deprotection reaction are: dissolving the terminal protection intermediate in an organic solvent, and deprotecting under the action of acid in ice bath or at room temperature to activate the functional group;
the cycle times of the coupling reaction and the deprotection reaction are more than or equal to 1.
4. The method for synthesizing a metal-backbone polymer having a precise length according to claim 3, wherein the organic solvent is selected from toluene, pyridine, picoline, 1, 4-dioxane, dichloromethane, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, or xylene;
the palladium catalyst is selected from tris (dibenzylideneacetone) dipalladium, palladium acetate, (2-dicyclohexylphosphine-3, 6-dimethoxy-2 ',4',6' -triisopropyl-1, 1' -biphenyl) [2- (2-aminoethylphenyl) ] palladium chloride, chloro (2-dicyclohexylphosphino-2 ' ',6' ' -diisopropyl-1, 1' ' -biphenyl) [2- (2-aminoethylphenyl) ] palladium (II) or dichloro [1,1' -bis (diphenylphosphino) ferrocene ] palladium;
the organophosphorus ligand is selected from 1, 3-bis (diphenylphosphine) propane, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl or dicyclohexyl [3, 6-dimethoxy-2 ',4',6' -triisopropyl [1,1' -biphenyl ] -2-yl ] phosphine;
the base is selected from potassium tert-butoxide, cesium carbonate, sodium tert-butoxide, diisopropylethylamine, sodium carbonate or potassium carbonate;
the acid is selected from glacial acetic acid, hydrochloric acid, hydrobromic acid or trifluoroacetic acid.
5. The method of claim 1, wherein the end-capping monomer in step (iii) has the following structural formula:
；
wherein n is more than or equal to 0, and X is one of fluorine, chlorine, bromine and iodine halogen atoms.
6. The method for synthesizing a metal-backbone polymer having an accurate length according to claim 1, wherein the metal salt compound is selected from acetate, chloride, bromide, sulfate or trifluoroacetate of a transition metal.
7. A metal main chain polymer with precise length, which is characterized by being prepared by the synthetic method according to any one of claims 1-6.
8. The use of a polymer having a metal main chain of a precise length according to claim 7, wherein the polymer is to be used in an optoelectronic material, a superconducting material or a biomedical material.
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