CN114773396B - Terpyridine platinum (II) complex and preparation method and application thereof - Google Patents
Terpyridine platinum (II) complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN114773396B CN114773396B CN202210460402.4A CN202210460402A CN114773396B CN 114773396 B CN114773396 B CN 114773396B CN 202210460402 A CN202210460402 A CN 202210460402A CN 114773396 B CN114773396 B CN 114773396B
- Authority
- CN
- China
- Prior art keywords
- complex
- platinum
- terpyridyl
- reaction
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 51
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 229910020366 ClO 4 Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000008282 halocarbons Chemical class 0.000 claims description 9
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001338 self-assembly Methods 0.000 abstract description 28
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000002244 precipitate Substances 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 16
- 239000003446 ligand Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000004809 thin layer chromatography Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- -1 isooctyl Chemical group 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 11
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- QSACPWSIIRFHHR-UHFFFAOYSA-N dimethylphenyl isocyanide Natural products CC1=CC=CC(C)=C1C#N QSACPWSIIRFHHR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- YQLRKXVEALTVCZ-UHFFFAOYSA-N 2-isocyanato-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1N=C=O YQLRKXVEALTVCZ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N isonitrile group Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- DNJLFZHMJDSJFN-UHFFFAOYSA-N 2-isocyano-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1[N+]#[C-] DNJLFZHMJDSJFN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical group C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 description 1
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229940125907 SJ995973 Drugs 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- FKCBLVCOSCZFHV-UHFFFAOYSA-N acetonitrile;ethanol Chemical compound CCO.CC#N FKCBLVCOSCZFHV-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- XZMHJYWMCRQSSI-UHFFFAOYSA-N n-[5-[2-(3-acetylanilino)-1,3-thiazol-4-yl]-4-methyl-1,3-thiazol-2-yl]benzamide Chemical compound CC(=O)C1=CC=CC(NC=2SC=C(N=2)C2=C(N=C(NC(=O)C=3C=CC=CC=3)S2)C)=C1 XZMHJYWMCRQSSI-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a terpyridine platinum (II) complex, a preparation method and application thereof. Wherein, the terpyridyl platinum (II) complex has the following structural general formula:r1 is selected from H, substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; r2 is selected from substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; x is X ‑ Selected from PF 6 ‑ 、BF 4 ‑ 、OSO 2 CF 3 ‑ And ClO 4 ‑ . The terpyridyl platinum (II) complex of the invention can realize: the self-assembly is driven by the intermolecular anion-pi acting force, so that the self-assembly body with various different morphologies can be easily regulated and controlled; the energy of d-d state existing in the molecule is improved, and the luminous efficiency is enhanced; the luminous wavelength can be regulated and controlled under the action of different solvent systems.
Description
Technical Field
The invention relates to the technical field of platinum complexes, in particular to a terpyridine platinum (II) complex, a preparation method and application thereof.
Background
The unique molecular structure of the planar square platinum (ii) complex imparts its rich optical properties and excellent assembly properties. Among them, the terpyridyl platinum (II) complex is the most common one, and has remarkable advantages in the aspects of molecular assembly and regulation and control of optical properties, so that the terpyridyl platinum (II) complex plays a more important role in the fields of organic luminescent materials, medicine and the like. However, the conventional terpyridyl platinum (II) complex has the following problems: firstly, the luminous quantum efficiency is low, the luminous wavelength is often regulated and controlled by a modifying ligand, and the luminescence is weak; if the luminescence wavelength is changed, the ligand is usually redesigned, and the synthesis is difficult. Secondly, the self-assembly driving force of the terpyridyl platinum (II) complex is relatively single, and the self-assembly is mainly driven by intermolecular pi-pi accumulation or Pt … Pt interaction, so that a one-dimensional structure assembly is easy to form under the effect of supermolecules, and the morphology of the assembly is difficult to regulate.
Accordingly, the prior art is still further developed and improved.
Disclosure of Invention
The invention aims to solve the technical problems that the existing terpyridyl platinum (II) complex has poor luminous performance and is difficult to regulate and control the morphology during self-assembly.
The invention solves the technical problems by the following technical proposal:
in a first aspect, the invention provides a terpyridyl platinum (II) complex based on terpyridyl platinum (II) by reasonably designing a ligand and regulating anions, wherein the terpyridyl platinum (II) complex has the following structural general formula:
wherein R1 is selected from one of H, substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; r2 is selected from one of substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; x is X - Selected from PF 6 - 、BF 4 - 、OSO 2 CF 3 - And ClO 4 - One of them.
In a second aspect, the present invention provides a process for the preparation of a terpyridyl platinum (ii) complex as described above, wherein the process comprises:
reflux reaction is carried out on the first intermediate and dichloro-di (dimethyl sulfoxide) platinum in a halogenated hydrocarbon solvent to obtain a second intermediate; wherein the structural formula of the first intermediate isThe structural formula of the second intermediate is +.>
Reacting the second intermediate, R2-NC and MX in a polar solvent to obtain the terpyridyl platinum (II) complex; the MX is AgX or KX.
Optionally, the preparation method of the terpyridyl platinum (II) complex comprises the step of preparing the terpyridyl platinum (II) complex by using at least one of dichloromethane and chloroform as the halogenated hydrocarbon solvent.
Optionally, the preparation method of the terpyridyl platinum (II) complex comprises the steps of carrying out reflux reaction at 50-110 ℃ for 6-24h.
Optionally, the preparation method of the terpyridyl platinum (II) complex comprises the following steps of: 1-1.2mmol:40-60mL.
Optionally, the preparation method of the terpyridyl platinum (ii) complex, wherein the preparation method of the first intermediate comprises the following steps:
heating R1-CHO, 2-acetyl pyridine, 28% ammonia water and strong alkali in an alcohol solvent for reaction to obtain a first intermediate;
the strong base is potassium hydroxide and/or sodium hydroxide; the alcohol solvent is at least one of methanol, ethanol and propanol; the heating temperature of the heating reaction is 30-50 ℃.
Optionally, the preparation method of the terpyridyl platinum (II) complex comprises the step of preparing the terpyridyl platinum (II) complex by using a polar solvent selected from one or more of methanol, ethanol, propanol, dimethyl sulfoxide and acetonitrile.
Optionally, the preparation method of the terpyridyl platinum (II) complex comprises the following steps of: 1.5-3.5mmol:6-18mmol:900-4200mL.
In a third aspect, the present invention provides a self-assembled material, wherein the self-assembled material comprises a terpyridyl platinum (II) complex as described above.
In a fourth aspect, the present invention provides a luminescent material, wherein the luminescent material comprises a terpyridyl platinum (II) complex as described above.
The beneficial effects are that: compared with the prior art, the invention introduces the isonitrile auxiliary ligand and some specific anions based on the terpyridine platinum (II), designs the substituent R1 on the terpyridine and the substituent R2 on the isonitrile group, and obtains the terpyridine platinum (II) complex (namely the target complex) with the general structural formula. On one hand, the introduction of the substituent can effectively change the electron distribution of the ligand, and the luminous efficiency of the target complex is improved under the dual actions of the charge transfer (Metal to Ligand Charge Transfer, MLCT) from metal to the ligand and the charge transfer (auxiliary ligands to terpyridine ligandsCharge transfer, LLCT) from the auxiliary ligand to the terpyridine ligand; on the other hand, by changing anions with different electron withdrawing capacities, the electron delocalization of the platinum complex can be effectively changed, and further the effective regulation and control of the luminous wavelength can be realized; in addition, the steric hindrance and the twisting configuration of the R1 substituent can reasonably regulate and control the dynamics and the thermodynamic behavior of the self-assembly of the target compound under different solvent systems, and the parent nucleus of the substituent and the target complex can be effectively regulated and controlledThe competition mechanism can also realize the regulation and control of the assembly behavior of the target compound, and can obtain self-assemblies with various different morphologies (such as one-dimensional rod shape, two-dimensional sheet shape and three-dimensional sphere shape). Therefore, the terpyridine platinum (II) complex provided by the invention provides an important basis for expanding the assembly strategy of the platinum (II) complex, and the obtained self-assembled body has potential application in the fields of cell imaging, chemical catalysis, photocatalysis, electrocatalysis and the like.
Drawings
FIG. 1 a) is a Scanning Electron Microscope (SEM) image of the assembly of the complex (9) according to the example of the present invention in pure water to produce a precipitate; b) Is a Transmission Electron Microscope (TEM) image of the complex (9) assembled in pure water to produce a precipitate; c) Is a fluorescence microscopic image of the complex (9) assembled in pure water to generate a precipitate;
FIG. 2 is a graph showing the X-ray diffraction pattern of the complex (9) in powder state and self-assembled in pure water to produce precipitate;
in FIG. 3 a-b) are the complexes TPE-TPy-Pt-NC-Ph/PF 6 Respectively at H 2 O and H 2 Scanning electron microscopy of the assembly in O/acn=9/1 to produce a precipitate (where the amount of mother liquor added is 0.1 mL); c-d) is the corresponding transmission electron microscopy image;
FIG. 4 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 Scanning electron microscopy of the precipitate produced by assembly in EtOH (where the amount of mother liquor added was 0.1 mL);
FIG. 5 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 In EtOH/H 2 Scanning electron microscopy of the assembly in o=2/8 to produce a precipitate (wherein the amount of mother liquor added is 0.1 mL);
FIG. 6 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 In EtOH/H 2 Scanning electron microscopy images of the assembly in o=1/9 to produce a precipitate (where the amount of mother liquor added was 0.1 mL);
FIG. 7 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 Transmission electron microscopy in EtOH (400 nm);
FIG. 8 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 Transmission electron microscopy in EtOH (10 nm);
FIG. 9 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 A corresponding selective electron diffraction pattern in EtOH;
in FIG. 10 e) is the complex TPE-TPy-Pt-NC-Ph/PF 6 At H 2 Assembling in O to generate a selective electron diffraction pattern corresponding to precipitation; f) Is a complex TPE-TPy-Pt-NC-Ph/PF 6 At H 2 Assembling in O/ACN=9/1 to generate a selective electron diffraction diagram corresponding to precipitation;
FIG. 11 is a diagram of a complex TPE-TPy-Pt-NC-Ph/PF 6 X-ray diffraction contrast diagram of sediment generated by self-assembly in powder state and water and ethanol system respectively;
FIG. 12 shows the crystal structure of complex 4 c.
Detailed Description
The invention provides a terpyridine platinum (II) complex, a preparation method and application thereof, and aims to make the purposes, technical schemes and advantages of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides the following technical scheme for solving the problems that the existing terpyridyl platinum (II) complex has poor luminous performance and the appearance is not easy to regulate and control during self-assembly.
In a first aspect, the invention provides a terpyridyl platinum (II) complex having the following structural formula:wherein R1 is selected from one of H, substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; r2 is selected from one of substituted or unsubstituted chain alkyl and substituted or unsubstituted aromatic alkyl; x is X - Selected from PF 6 - 、BF 4 - 、OSO 2 CF 3 - And ClO 4 - One of them.
In this embodiment, with terpyridine platinum (ii) as a core, the target complex obtained by introducing an isocyanide auxiliary ligand and a specific anion and adjusting and controlling the substituent R1 on the terpyridine ligand and the substituent R2 on the isocyanide auxiliary ligand can be realized: on the one hand, self-assembly can be driven by the interaction of anions and pi among molecules during self-assembly, and the intermolecular acting force is easy to regulate and control in a self-assembly system, so that self-assembly bodies with various different morphologies can be obtained through self-assembly; on the other hand, the energy of d-d state existing in the molecule can be improved, and the luminous efficiency is enhanced; the light-emitting wavelength of the light-emitting diode can be regulated and controlled under the action of different solvent systems. .
Optionally, the substituted or unsubstituted chain hydrocarbon group contains 1 to 20 carbon atoms; specifically, the substituted chain hydrocarbon group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, isohexyl, isooctyl, isodecyl, isododecyl, isohexadecyl, isooctyl, and the like; the unsubstituted chain hydrocarbon groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, and the like.
Optionally, the substituted or unsubstituted aromatic hydrocarbon group contains 6 to 20 carbon atoms, specifically, the substituted aromatic hydrocarbon group includes but is not limited to Etc.; the unsubstituted aromatic hydrocarbon group includes but is not limited to +.> Etc. It should be understood that in the structural formula of the substituent, the substitution positions of R1 and R2 are marked by dotted lines.
Preferably, R1 is H,R2 is->The terpyridyl platinum (II) complex may be, for example> Etc.
In a second aspect, based on the same inventive concept, the present invention also provides a method for preparing a terpyridyl platinum (ii) complex as described above, wherein the method comprises:
reflux reaction is carried out on the first intermediate and dichloro-di (dimethyl sulfoxide) platinum in a halogenated hydrocarbon solvent to obtain a second intermediate; wherein the structural formula of the first intermediate isThe structural formula of the second intermediate is +.>
Reacting the second intermediate, R2-NC and MX in a polar solvent to obtain the terpyridyl platinum (II) complex; the MX is AgX or KX.
Specifically, the method may include the steps of:
step one, according to the reaction typeUnder the protection of inert gas, R1-CHO, 2-acetyl pyridine, 28% ammonia water and strong alkali are heated in alcohol solvent for reaction, and after the reaction is finished, the first intermediate R1-TPy is obtained through purification.
In some embodiments, in step one, the inert gas is one of nitrogen, argon, and helium; the strong base is at least one of KOH and NaOH; the alcohol solvent is at least one of methanol, ethanol and propanol; the temperature of the heating reaction is 30-50 ℃ (such as 40 ℃), and the time of the heating reaction is 6-24h (such as 18 h); the addition ratio of R1-CHO, 2-acetylpyridine, 28% ammonia water, strong alkali and alcohol solvent is 1mmol:3.05-4mmol:4-5mL:3.5-5mmol:10-15mL; illustratively, the R1-CHO, 2-acetylpyridine, 28% ammonia, strong base, alcohol solvent feed ratio is 1mmol:3.2mmol:4.3mL:4mmol:14.3mL.
Step two, according to the reaction type
Under the protection of inert gas, the first intermediates R1-TPy and (DMSO) 2 PtCl 2 And (DMSO is dimethyl sulfoxide) in a hydrocarbon solvent for reflux reaction, and purifying after the reaction is finished to obtain a second intermediate R1-TPy-Pt-Cl.
In some embodiments, in step one, the inert gas is one of nitrogen, argon, and helium; the halogenated hydrocarbon solvent is at least one of dichloromethane and chloroform; the temperature of the reflux reaction is 50-110 ℃ (such as 90 ℃), and the time of the reflux reaction is 6-24h (such as 20 h); R1-TPy, (DMSO) 2 PtCl 2 The feed ratio of the halogenated hydrocarbon solvent is 1mmol:1-1.2mmol:40-60mL, preferably R1-TPy, (DMSO) 2 PtCl 2 The feed ratio of the halogenated hydrocarbon solvent is 1mmol:1mmol:56mL.
Step three, according to the reaction type
The second intermediate R1-TPy-Pt-Cl and R2-NC (R2-NC is) And (3) carrying out room temperature reaction on MX in a polar solvent, and purifying after the reaction is finished to obtain a target complex R1-TPy-Pt-CN-R2/X.
In some embodiments, in step three, the polar solvent is at least one of methanol, ethanol (EtOH), propanol, dimethyl sulfoxide (DMSO), and Acetonitrile (ACN); MX is AgX or KX; the addition ratio of R1-TPy-Pt-Cl, R2-NC, MX and polar solvent is 1mmol:1.5-3.5mmol:6-18mmol:900-4200mL, for example, R1-TPy-Pt-Cl, R2-N≡CH, MX, polar solvent may be added in a ratio of 1mmol:3mmol:9mmol:1000mL, 1mmol:2.5mmol:15mmol:2083mL, 1mmol:2.5mmol:15mmol:4166mL, 1mmol:2mmol:6.5mmol:1136mL, etc.
In a third aspect, based on the same inventive concept, the present invention provides a self-assembled material, wherein the self-assembled material comprises a terpyridyl platinum (ii) complex as described above.
In a fourth aspect, based on the same inventive concept, the present invention provides a luminescent material, wherein the luminescent material comprises a terpyridyl platinum (ii) complex as described above. The invention is further illustrated by the following examples.
Four different anionic terpyridyl platinum (II) complexes (TPE-TPy-Pt-CN-Ph/SO) 3 CF 3 、TPE-TPy-Pt-CN-Ph/BF 4 、TPE-TPy-Pt-CN-Ph/PF 6 、TPE-TPy-Pt-CN-Ph/ClO 4 ) The general route of synthesis of (2) is as follows:
the method comprises the steps of carrying out a first treatment on the surface of the See examples 1-5 for specific preparation procedures.
Example 1
Wherein, the synthesis of 4- (1, 2-triphenylvinyl) benzaldehyde (1):
to a 250mL two-necked flask, bromotriphenylethylene (2.00 g,5.97 mmol) and 4-formylphenylboronic acid (1.16 g,7.76 mmol) were added, and the vacuum-nitrogen operation was repeated three times, followed by adding 100mL of analytically pure tetrahydrofuran under nitrogen protection, and stirring for dissolution. Potassium carbonate (4.95 g,35.79 mmol) was dissolved in 14mL of ultrapure water, and the mixture was added to a two-necked flask under nitrogen protection, followed by bubbling for 45min, and then tetrakis (triphenylphosphine) palladium (0.55 g,0.48 mmol) was sequentially added thereto, and heated to 80℃under reflux overnight. The progress of the reaction was monitored by Thin layer chromatography (Thin-layer chromatography, TLC), cooled to room temperature after completion of the reaction, and deionized water was added. The aqueous phase was extracted with dichloromethane, the organic extracts were combined and dried over anhydrous magnesium sulfate, and the crude product concentrated under reduced pressure was purified by flash column chromatography on a silica gel column to give product 1 (1.98 g, 92%). 1 H NMR(CDCl 3 ,600MHz,δ/ppm):9.92(s,1H),7.64(d,J＝8.4Hz,2H),7.22(d,J＝7.8Hz,2H),7.14(t,J＝6.6Hz,9H),7.06-7.02(m,6H). 13 C NMR(CDCl 3 ,125MHz,δ/ppm)δ191.9,150.6,143.0,142.9,139.8,134.3,132.0,131.3,131.2,129.2,127.9,127.8,127.1,126.9.
Synthesis of 4'- (4- (1, 2-triphenylvinyl) phenyl) -2,2':6', 2' -pyridine (2):
to a 100mL two-necked flask, compound 1 (1.01 g,2.8 mmol) was added, and the vacuum-nitrogen-introducing operation was repeated three times, followed by adding 40mL of ethanol, stirring to dissolve, then sequentially adding 2-acetylpyridine (1 mL,9 mmol), 28% aqueous ammonia (12 mL), potassium hydroxide (0.63 g,11.21 mmol), and heating to 40℃and refluxing overnight. TLC (thin layer chromatography) monitors the reaction progress, after the reaction is complete, suction filtration is performed, and the obtained filter cake is repeatedly washed with analytically pure ethanol and dried in a vacuum drying oven for one night, so that the product 2 (0.62 g, 40%) is obtained. 1 H NMR(CDCl 3 ,600MHz,δ/ppm):8.74(dd,J＝0.6,0.6Hz,2H),8.71(s,2H),8.70(s,1H),8.68(s,1H),7.91(ddd,J＝1.2,1.8,1.8Hz,2H),7.69(d,J＝8.4Hz,2H),7.38(dddd,J＝1.2,1.2,12,1.2Hz,2H),7.20(s,1H),7.19(s,1H),7.16-7.14(m,8H),7.12-7.09(m,7H). 13 C NMR(CDCl 3 ,150MHz,δ/ppm)δ156.1,155.6,150.0,149.0,144.8,143.6,143.5,141.6,140.3,137.1,136.2,132.0,131.4,131.3,127.9,127.8,127.7,126.7,126.6,126.6,126.5,123.9,121.4,118.8.MALDI-TOF-MS:m/zcalcd for[C 41 H 29 N 3 ] + :563.24,found:564.24[M+1] + .
(DMSO) 2 PtCl 2 (abbreviated as compound a) synthesis:
to a 100mL two-necked flask, potassium chloroplatinite (1.00 g,2.41 mmol) was charged, the operation of evacuation-nitrogen introduction was repeated three times, 5mL deionized water was added under nitrogen protection, and stirring was performed to dissolve, then DMSO (1 mL,42.53 mmol) was added, and the reaction was carried out at room temperature for 24 hours. A white precipitate formed, which was filtered off with suction and the filter cake was dried in vacuo to give Compound A (1.7 g, 84%).
Synthesis of Complex TPE-TPy-Pt-Cl (abbreviated as Complex 3):
into a 100mL two-necked flask, compound 2 (0.50 g,0.89 mmol) and (DMSO) were charged 2 PtCl 2 (0.37 g,0.89 mmol), the vacuum-nitrogen-introducing operation was repeated three times, 50mL of chloroform was added under nitrogen protection, and the mixture was heated to 100℃and refluxedOvernight. TLC was used to monitor the progress of the reaction, after completion of the reaction, the filter cake obtained was repeatedly washed with analytically pure ethanol and dried in a vacuum oven for one night to give Complex 3 (0.36 g, 54%). 1 H NMR(DMSO,600MHz,δ/ppm):8.84(s,2H),8.80(d,J＝8.4Hz,2H),8.60(t,J＝3.0Hz,2H),8.36(t,J＝7.8Hz,2H),8.02(d,J＝8.4Hz,2H),7.76(t,J＝6.0Hz,2H),7.28-7.23(m,7H),7.21(d,J＝1.2Hz,1H),7.20(s,1H),7.19-7.17(m,2H),7.15-7.14(m,2H),7.10-7.08(m,2H),7.06-7.04(m,2H). 13 C NMR(DMSO,150MHz,δ/ppm)δ158.5,154.6,152.2,151.4,147.3,143.4,143.3,143.2,142.9,142.5,140.0,132.8,132.1,131.2,131.2,131.1,129.5,128.6,128.6,128.4,128.0,127.6,127.4,127.4,126.7,121.4.MALDI-TOF-MS:m/z calcd for[C 41 H 29 N 3 PtCl] + :793.17,found:794.17[M+1] + .
For the complex TPE-TPy-Pt-Cl, the ultraviolet absorption peak at 421nm in tetrahydrofuran occurs due to the molecules undergoing a charge transfer transition from platinum (II) to the ligand TPE-TPy [ dpi (Pt) →pi (TPy), MLCT]Is caused by the process in which the ligand-to-ligand charge transfer transition characteristic [ pi (TPE) →pi (TPy), LLCT also occurs]This process is called MLCT/LLCT. When poor solvent water was gradually added to the above solution, the ultraviolet absorption peak of the complex TPE-TPy-Pt-Cl at 421nm gradually decreased, while when the water content in the mixed solvent reached 80%, the ultraviolet absorption peak at 421nm was significantly decreased, accompanied by the formation of a red-shifted peak (lambda) max =456 nm), which is commonly referred to as metal-ligand charge transfer (MMLCT). This feature suggests the possibility of ground state aggregation and Pt.. Pt or pi-pi stacking interactions in high non-solvent content media. This suggests that the complex undergoes a self-assembly process in a non-solvent medium, resulting in the formation of Pt.. Pt or pi-pi stacking interactions. The ultraviolet absorption peak at 287nm is attributed to the spin transition [ pi→pi ]]。
Example 2
Complex TPE-TPy-Pt-CN-Ph/SO 3 CF 3 (abbreviated as complex 4 a) synthesis:
into a 500mL single-necked flask was chargedThe complex TPE-TPy-Pt-Cl (0.10 g,0.12 mmol) and 2, 6-dimethylphenyl isocyanide (0.04 g,0.30 mmol) were added with 250mL of acetonitrile, and after stirring well, silver triflate (0.30 g,1.8 mmol) was added and stirred overnight at ambient temperature. Monitoring the reaction progress by TLC, after the reaction is completed, filtering, spinning the filtrate to dryness, then dissolving the filtrate by using 1mL of dichloromethane, adding a large amount of diethyl ether into the filtrate to form red precipitate, filtering the precipitate, washing a filter cake by using dichloromethane and diethyl ether, and then drying the filter cake in vacuum to obtain the complex 4a (0.10 g, 75%). 1 H NMR(CD 3 CN,600MHz,δ/ppm):8.96(dd,J＝0.6Hz,1.2Hz,2H),8.63(dd,J＝0.6Hz,1.2Hz,2H),8.53(ddd,J＝1.2Hz,1.2Hz,1.2Hz,2H),7.91(tt,J＝1.8Hz,1.8Hz,1.8Hz,2H),7.86(dtd,J＝1.2Hz,1.8Hz,1.8Hz,2H),7.53(t,J＝7.8Hz,1H),7.42(d,J＝7.8Hz,2H),7.39(tt,J＝1.8Hz,J＝1.8Hz,2H),7.23-7.19(m,9H),7.18-7.14(m,4H),7.12-7.11(m,2H). 13 CNMR(CD 3 CN,150MHz,δ/ppm):158.0,156.5,155.2,148.3,143.1,143.0,139.8,137.2,132.6,132.3,131.8,131.0,131.0,130.8,130.4,129.0,128.8,128.5,128.0,127.8,127.6,127.0,126.9,126.6,125.9,122.2,121.9,120.1,18.1.MALDI-TOF-MS:m/z calcd for[C 50 H 38 N 4 Pt] + :889.27,found:889.27[M] + .
Example 3
Complex TPE-TPy-Pt-CN-Ph/BF 4 (abbreviated as complex 4 b):
to a 500mL single-necked flask were added the complex TPE-TPy-Pt-Cl (0.05 g,0.06 mmol) and 2, 6-dimethylphenyl isocyanate (0.02 g,0.15 mmol), 250mL acetonitrile was added, and after stirring well, silver tetrafluoroborate (0.30 g,0.9 mmol) was added and reacted overnight at room temperature. The progress of the reaction was monitored by TLC, after completion of the reaction was determined, filtration was performed, the filtrate was dried by spin-drying, then it was dissolved with 1mL of dichloromethane, a large amount of diethyl ether was added thereto, a red precipitate was precipitated, filtration was performed with a buchner funnel to obtain a cake, the obtained cake was washed with analytically pure dichloromethane, diethyl ether, and then the cake was dried in vacuo to obtain complex 4b (0.06 g, 94%). 1 H NMR(CD 3 CN,600MHz,δ/ppm):8.95(d,J＝5.4Hz,2H),8.61(s,2H),8.55-8.54(m,2H),7.89(d,J＝8.4Hz,2H),7.53(t,J＝7.8Hz,2H),7.42-7.38(m,5H),7.24-7.14(m,17H),2.65(s,6H). 13 C NMR(150MHz,CDCl 3 )δ158.0,156.5,155.1,148.3,143.2,143.1,143.0,142.8,139.8,137.2,132.5,132.3,131.8,131.0,130.8,130.4,128.5,127.8,127.6,127.0,126.9,126.6,121.9,18.0.MALDI-TOF-MS:m/zcalcd for[C 50 H 38 N 4 Pt] + :889.27,found:889.27[M] + .
Example 4
Complex TPE-TPy-Pt-CN-Ph/PF 6 (abbreviated as complex 4 c):
to a 500mL single-necked flask were added the complex TPE-TPy-Pt-Cl (0.18 g,0.22 mmol) and 2, 6-dimethylphenyl isocyanate (0.07 g,0.44 mmol), 250mL acetonitrile was added, and after stirring uniformly, silver hexafluorophosphate (0.36 g,1.43 mmol) was added and stirred overnight at room temperature. TLC monitors the progress of the reaction, after completion of the reaction, it was filtered, the filtrate was spin-dried, then it was dissolved with 1mL of analytically pure dichloromethane, a large amount of diethyl ether was added thereto, a red precipitate was precipitated, a filter cake was obtained by suction filtration with a Buchner funnel, the obtained red filter cake was washed with a large amount of analytically pure dichloromethane, diethyl ether, and then the filter cake was dried in vacuo to obtain complex 4c (0.2 g, 75%). 1 H NMR(CD 3 CN,600MHz,δ/ppm):8.96-8.95(m,2H),8.60(s,2H),8.54-8.53(m,4H),7.90(t,J＝3.6Hz,1H),7.88(t,J＝4.2Hz,1H),7.86-7.84(m,2H),7.53(t,J＝7.8Hz,1H),7.43-7.38(m,4H),7.23-7.11(m,17H). 13 CNMR(CD 3 CN,150MHz,δ/ppm):158.02，156.5,156.3,155.1,148.3,143.8,143.2,143.1,143.0,139.8,137.2,132.6,132.3,131.8,131.0,130.8,130.4,128.5,128.0,127.8,127.6,127.0,126.9,126.5,121.9,18.0.MALDI-TOF-MS:m/z calcd for[C 50 H 38 N 4 Pt] + :889.27,found:889.27[M] + .
Example 5
Complex TPE-TPy-Pt-CN-Ph/ClO 4 (abbreviated as complex 4 d):
to a 500mL single-necked flask were added the complex TPE-TPy-Pt-Cl (0.05 g,0.06 mmol) and 2, 6-dimethylphenyl isocyanate (0.02 g,0.15 mmol), 250mL acetonitrile was added, and after stirring well, silver perchlorate (0.19 g,0.9 mmol) was added and reacted overnight at room temperature.The progress of the reaction was monitored by TLC, after the reaction had been completed, the filtrate was filtered, dried by spin-drying, then dissolved with 1mL of analytically pure dichloromethane, to which a large amount of diethyl ether was added, a red precipitate was formed, suction filtered, the filter cake was washed with dichloromethane, diethyl ether, and then the filter cake was dried in vacuo to give complex 4d (0.49 g, 69%). 1 H NMR(CD 3 CN,500MHz,δ/ppm):8.96(d,J＝5.5Hz,2H),8.60(s,2H),8.55-8.51(m,4H),7.89(d,J＝8.5Hz,2H),7.87-7.84(m,2H),7.53(t,J＝8.0Hz,1H),7.43-7.39(m,4H),7.25-7.11(m,17H),2.66(s,6H). 13 CNMR(CD 3 CN,150MHz,δ/ppm):158.02，156.5,156.3,155.1,148.3,143.8,143.2,143.1,143.0,139.8,137.2,132.6,132.3,131.8,131.0,130.8,130.4,128.5,128.0,127.8,127.6,127.0,126.9,126.5,121.9,18.0.MALDI-TOF-MS:m/z calcd for[C 50 H 38 N 4 Pt] + :889.27,found:889.27[M] + .
Like complex 3, complexes 4a-4d are also non-fluorescent in pure solution at room temperature, but they are observed to fluoresce red under 365nm ultraviolet light in the solid state, and their luminous efficiency is also greater than that of complex 3, and their absolute quantum yields (. Phi.) can be obtained by testing the quantum yields of complexes 4a-4d F ) 1.1%, 2.3%, 4.4%, 1.3%, respectively, complex 3 (. Phi.) respectively F 0.1%) of the fluorescent material is 11, 23, 44 and 13 times, the luminous efficiency is obviously improved, and the process from fluorescence quenching to fluorescence generation of the material is realized. Namely, by modifying the complex 3, the luminescence thereof can be enhanced.
At the same time, the solid state of these molecules was tested with the aid of an ultraviolet-near infrared visible spectrophotometer and a fluorescence spectrometer. Wherein, the data of the ultraviolet diffuse reflection can obtain that the complexes 4a-4d begin to reflect at 423nm, 517nm, 500nm and 430nm respectively, so that 423nm, 517nm, 500nm and 430nm are selected as excitation wavelengths respectively to study the emission spectrum. The maximum emission wavelengths of complexes 4a-4d were at 588nm, 626nm, 581nm and 558nm, respectively. The regulation and control of the luminous wavelength can be realized through modification of simple anions.
Example 6
Complex Ph-TPy-Pt-CN-Ph/PF 6 、TPy-Pt-CN-Ph/PF 6 The synthesis route is as follows:
synthesis of 4 '-phenyl-2, 2':6', 2' -terpyridine (abbreviated as Complex 5):
to a 100mL two-necked flask, benzaldehyde (1.00 g,9.42 mmol) was added, and the flask was evacuated and purged with nitrogen three times, 30mL of ethanol was added under nitrogen protection, and the mixture was stirred uniformly, followed by sequential addition of 2-acetylpyridine (5 mL,45 mmol), 28% aqueous ammonia (20 mL), potassium hydroxide (2.11 g,37.69 mmol) and heating to 40℃and refluxing overnight. TLC (thin layer chromatography) monitors the reaction progress, after the reaction is complete, suction filtration is performed, and the obtained filter cake is repeatedly washed with analytically pure ethanol and dried in a vacuum drying oven for one night, so that complex 5 (2.62 g, 90%) is obtained. 1 H NMR(CDCl 3 ,500MHz,δ/ppm):8.74-8.72(m,4H),8.66(d,J＝8.0Hz,2H),7.91-7.90(m,2H),7.88-7.85(m,2H),7.52-7.49(m,2H),7.46-7.43(m,1H),7.35-7.32(m,2H). 13 C NMR(CDCl 3 ,125MHz,δ/ppm)δ156.2,155.9,150.3,149.1,138.5,136.9,129.0,128.9,127.3,123.8,121.4,118.9.MALDI-TOF-MS:m/z calcd for[C 21 H 15 N 3 ] + :309.13,found:310.13[M+1] + .
Synthesis of Complex Ph-TPy-Pt-Cl (abbreviated as Complex 6):
into a 100mL two-necked flask, complex 5 (0.10 g,0.32 mmol) and (DMSO) were added 2 PtCl 2 (0.14 g,0.32 mmol) was evacuated-purged with nitrogen three times repeatedly, then 50mL of dry chloroform was added, and the mixture was heated to 100℃and refluxed overnight for reaction. TLC was used to monitor the progress of the reaction, after completion of the reaction, suction filtration was performed, and the cake was washed with ethanol and dried under vacuum to give Compound 6 (0.15 g, 88%). 1 H NMR(DMSO,600MHz,δ/ppm):9.03(d,J＝11.4Hz,2H),8.98-8.89(m,4H),8.58-8.54(m,2H),8.22(s,2H),7.96(s,2H),7.69(s,3H).MALDI-TOF-MS:m/z calcd for[C 21 H 15 N 3 PtCl] + :539.06,found:540.06[M+1] + .
Complex Ph-TPy-Pt-NC-Ph/PF 6 (abbreviated as complex 7) synthesis:
to a 250mL single-necked flask, the complex Ph-TPy-Pt-Cl (0.05 g,0.09 mmol) and 2, 6-dimethylphenyl isocyanate (0.04 g,0.30 mmol) were added, 100mL of acetonitrile was added, and after stirring uniformly, silver hexafluorophosphate (0.1.5 g,0.9 mmol) was added and stirring was continued overnight at room temperature. TLC monitors the progress of the reaction, after completion of the reaction, the filtrate was filtered, dried by spin-drying, and then completely dissolved with 1mL of dried dichloromethane, to which a large amount of diethyl ether was added, and a red precipitate was precipitated, and the obtained cake was suction-filtered with a Buchner funnel, repeatedly washed with a large amount of dichloromethane and diethyl ether, and then dried under vacuum to obtain complex 7 (0.07 g, 88%). 1 H NMR(CD 3 CN,600MHz,δ/ppm):9.22(d,J＝6.0Hz,2H),9.18(s,2H),9.01(d,J＝8.4Hz,2H),8.68(t,J＝7.8Hz,2H),8.27(d,J＝8.4Hz,2H),8.18-8.16(m,2H),7.97-7.95(m,2H),7.74(t,J＝9.6Hz,2H),7.45(d,J＝7.8Hz,2H),2.62(s,6H).MALDI-TOF-MS:m/z calcd for[C 30 H 24 N 4 Pt] + :635.16,found:635.16[M] + .
Synthesis of Complex TPy-Pt-Cl (abbreviated as Complex 8):
into a 100mL two-necked flask was charged 2,2':6',2 "-terpyridine (0.20 g,0.86 mmol), (DMSO) 2 PtCl 2 (0.36 g,0.86 mmol) was evacuated-purged with nitrogen three times repeatedly, then 50mL of dry chloroform was added, and the mixture was heated to 100deg.C and refluxed overnight for reaction. TLC was used to monitor the progress of the reaction, after completion of the reaction, suction filtration was performed, and the cake was washed with ethanol and dried under vacuum to give product 6 (0.40 g, 93%). 1 H NMR(DMSO,600MHz,δ/ppm):8.92(d,J＝6.0Hz,2H),8.68-8.65(m,4H),8.64-8.61(m,1H),8.52(t,J＝7.8Hz,2H),7.97(t,J＝6.6Hz,2H).MALDI-TOF-MS:m/z calcd for[C 15 H 11 N 3 PtCl] + :463.03,found:463.03[M] + .
Complex TPy-Pt-NC-Ph/PF 6 (abbreviated as complex 9) synthesis:
into a 250mL single-necked flask, a mixture of TPy-Pt-Cl (0.05 g,0.10 mmol) and 2, 6-dimethylphenyl isocyanide (0.04 g,0.30 mmol) was added, 100mL of acetonitrile was added, and the mixture was stirred uniformlyAfter homogenization, silver hexafluorophosphate (0.15 g,0.9 mmol) was added and stirred overnight at ambient temperature. TLC monitors the progress of the reaction, after completion of the reaction, the filtrate was filtered, dried by spin-drying, and then completely dissolved with 1mL of dried dichloromethane, to which a large amount of diethyl ether was added, and a red precipitate was precipitated, and the obtained cake was suction-filtered with a Buchner funnel, repeatedly washed with a large amount of dichloromethane and diethyl ether, and then dried under vacuum to obtain complex 9 (0.07 g, 88%). 1 H NMR(CD 3 CN,600MHz,δ/ppm):9.20(d,J＝6.0Hz,2H),8.79(t,J＝6.0Hz,4H),8.63(t,J＝7.2Hz,3H),7.95-7.92(m,2H),7.54(t,J＝7.2Hz,1H),7.44(d,J＝7.8Hz,2H). 13 C NMR(CDCl 3 ,150MHz,δ/ppm)δ158.6,154.0,153.6,143.5,143.2,142.5,129.3,126.5,126.2,125.0,124.2,18.1.MALDI-TOF-MS:m/zcalcd for[C 24 H 20 N 4 Pt] + :559.13,found:559.13[M] + .
Complex TPy-Pt-NC-Ph/PF 6 (namely, complex 9) in a system of water/acetonitrile and water/ethanol, after 48 hours, only a self-assembled body was generated in pure water, and as shown in fig. 1 a), complex 9 was assembled into a self-assembled body having a very large length and diameter in pure water, the diameter was about 4500nm (fig. 1 b), and the luminescence color was yellow (fig. 1 c). By analysis of the X-ray diffraction of the complex 9 in a powder state and in the assembly in pure water to produce precipitation, we can obtain a strong and sharp diffraction peak of the self-assembly produced in pure water as shown in FIG. 2, which indicates that the molecules of the complex 9 are indeed aligned in a more orderly direction in pure water, and self-assembly occurs.
The following is a complex TPE-TPy-Pt-NC-Ph/PF prepared in example 4 above 6 (i.e., complex 4 c) was studied for self-assembly properties.
Preparation of the samples: weigh 2mg of TPE-TPy-Pt-NC-Ph/PF 6 This was dissolved in 2mL of acetonitrile solution as a mother liquor. The solution systems shown in tables 1 and 2 were configured. The specific operation is as follows: according to table 1 (table 2), mixed solutions of acetonitrile (ethanol) and water in different proportions were prepared, and the mother liquor was added and mixed uniformly, followed by standing for 24 hours.
TABLE 1 Complex TPE-TPy-Pt-NC-Ph/PF 6 Assembly test under acetonitrile/water system
TABLE 2 Complex TPE-TPy-Pt-NC-Ph/PF 6 Assembly test under ethanol/water System
Dropping the sample onto a silicon wafer, sucking away excessive solution, drying overnight in an oven, and then carrying out Scanning Electron Microscope (SEM) test on the sample; the same sampling method, the sample is dripped on a copper mesh covered with thin pure carbon, and then a projection electron microscope (TEM) test is carried out on the sample; similarly, the sample was dropped onto a round quartz plate, and the excess solution was sucked away with filter paper, and subjected to a fluorescence microscope test.
For complex 4c at H 2 Self-assembly in O/ACN systems was studied. A series of samples were prepared according to Table 1, and after standing for 24 hours, it was found that precipitates were present in the pure water and acetonitrile/water 1/9 samples, and the test results obtained by SEM and TEM were shown in FIGS. 3 a-b and c-d, respectively, and it was found that the self-assembled body morphology of the complex 4c obtained by self-assembling in the pure water and acetonitrile/water 1/9 system was a regular solid pellet, and the diameters of the pellets were 500-600nm and 200-300nm, respectively.
A series of samples were prepared according to Table 2, and after 24 hours of standing, it was found that in addition to precipitation in pure water, precipitation was observed in both ethanol and water/ethanol at 9/1 and 8/2, the morphology was observed by SEM, and in ethanol, a regular shape flake (as shown in FIG. 4) was observed in water: ethanol=8:2 in the solvent, the irregularly shaped flakes (shown in fig. 5), while water: ethanol=9: 1 are folded sheets (as shown in fig. 6). Namely, the difference of the polarity and the solubility of the solvent can affect the acting force and the speed in the self-assembly process, thereby having the regulation and control function on the appearance of the self-assembly body.
The self-assembly in ethanol was studied by TEM, the lamellar structure of which can be seen from fig. 7, the region being enlarged, the presence of the crystal lattice of which can be seen clearly (as shown in fig. 8), and the crystallinity of which can be seen to be high by selective electron diffraction (SAED) (as shown in fig. 9); (e and f in FIG. 10 are SAED patterns of self-assembly of complex 4c in water, acetonitrile/water 9/1, respectively), it is clear that: the good crystallinity of complex 4c in ethanol systems compared to complex 4c in water, acetonitrile/water 9/1 systems suggests that compound 4c does self-assemble into a sheet structure in ethanol, whereas it is a sphere structure in water, acetonitrile/water 9/1 systems. .
Meanwhile, as shown in fig. 11, the complex 4c only has a very weak diffraction peak at 22 degrees in the powder state, the precipitate generated after the complex 4c self-assembles in the water system has stronger diffraction peaks at 7 degrees and 22 degrees, and the precipitate generated after the complex 4c self-assembles in the ethanol system has diffraction peaks at 7 degrees, 10 degrees, 12 degrees, 15 degrees, 20 degrees, 22 degrees and 25 degrees, which indicates that the precipitate generated by the complex 4c self-assembles in the ethanol system (namely, self-assemblies) has better crystallinity, which is consistent with the phenomenon.
For the crystal structure of complex 4c, as shown in FIG. 12, after modification of complex 3, the tetraphenyl ethylene moiety still has a large distorted structure in the molecule, and the dimethyl benzene linked to the isocyanide is also non-coplanar with the terpyridine-platinum moiety, with two anions (hexafluorophosphate groups) on either side of the terpyridine. The distance between platinum and platinum reachesThe anions in the molecule are just positioned between two adjacent terpyridine planes, wherein F-H interaction is generated between the fluoride ions in the hexafluorophosphate radical and the hydrogen ions on the benzene ring, so that the molecules have stronger interactionThe function is achieved, so that a good self-assembly effect can be achieved.
Four different anion complexes (4 a-4 d) are obtained by adopting a triple bond to modify the complex TPE-TPy-Pt-Cl, so that the obvious improvement of the luminous quantum efficiency and the regulation and control of the luminous wavelength are realized. And then, the target product is subjected to self-assembly research, and the regulation and control of different morphologies of the self-assembly body are realized through the regulation and control of the solvent. Because the existence of tetraphenyl ethylene in the molecular structure breaks the platinum-platinum interaction, anions can be just embedded between molecules to drive the ordered arrangement of molecules through the anion-pi interaction, and the method provides a feasible strategy for constructing self-assemblies with different morphologies.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (8)
1. A terpyridyl platinum (II) complex is characterized by having the following structural general formula:
wherein X is - Selected from PF 6 - 、BF 4 - 、OSO 2 CF 3 - And ClO 4 - One of the following;
the R1 isR2 is->The substitution positions of R1 and R2 are marked by dotted lines.
2. A process for preparing a terpyridyl platinum (ii) complex according to claim 1, comprising:
reflux reaction is carried out on the first intermediate and dichloro-di (dimethyl sulfoxide) platinum in a halogenated hydrocarbon solvent to obtain a second intermediate; wherein the structural formula of the first intermediate isThe structural formula of the second intermediate is +.>
Reacting the second intermediate, R2-NC and MX in a polar solvent to obtain the terpyridyl platinum (II) complex; the MX is AgX or KX.
3. The method for producing a terpyridyl platinum (II) complex according to claim 2, wherein the halogenated hydrocarbon solvent is at least one of dichloromethane and chloroform.
4. The method for preparing terpyridyl platinum (II) complex according to claim 2, wherein the temperature of the reflux reaction is 50-110 ℃ and the time of the reflux reaction is 6-24h.
5. The method for preparing terpyridyl platinum (ii) complex according to claim 2, wherein the ratio of the first intermediate, dichloro-bis (dimethyl sulfoxide) platinum, and halogenated hydrocarbon solvent is 1mmol:1-1.2mmol:40-60mL.
6. The method for preparing a terpyridyl platinum (ii) complex according to claim 2, wherein the method for preparing the first intermediate comprises:
heating R1-CHO, 2-acetyl pyridine, 28% ammonia water and strong alkali in an alcohol solvent for reaction to obtain a first intermediate;
the strong base is potassium hydroxide and/or sodium hydroxide; the alcohol solvent is at least one of methanol, ethanol and propanol; the heating temperature of the heating reaction is 30-50 ℃.
7. The method for preparing a terpyridyl platinum (ii) complex according to claim 2, wherein the polar solvent is selected from one or more of methanol, ethanol, propanol, dimethyl sulfoxide and acetonitrile;
the charging ratio of the second intermediate, R2-NC, MX and the polar solvent is 1mmol:1.5-3.5mmol:6-18mmol:900-4200mL.
8. A self-assembled material comprising the terpyridyl platinum (ii) complex of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210460402.4A CN114773396B (en) | 2022-04-28 | 2022-04-28 | Terpyridine platinum (II) complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210460402.4A CN114773396B (en) | 2022-04-28 | 2022-04-28 | Terpyridine platinum (II) complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114773396A CN114773396A (en) | 2022-07-22 |
| CN114773396B true CN114773396B (en) | 2023-12-19 |
Family
ID=82435593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210460402.4A Active CN114773396B (en) | 2022-04-28 | 2022-04-28 | Terpyridine platinum (II) complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773396B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030783A (en) * | 2009-09-30 | 2011-04-27 | 中国科学院理化技术研究所 | One-dimensional micron or submicron material of metal organic platinum (II) coordination compounds and preparation method and application |
| CN113896904A (en) * | 2021-11-16 | 2022-01-07 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
| CN114031646A (en) * | 2021-11-26 | 2022-02-11 | 昆明理工大学 | Cyclometalated platinum complex and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8309304B2 (en) * | 2006-02-10 | 2012-11-13 | The University Of Hong Kong | Label-free optical sensing and characterization of biomolecules by d8 or d10 metal complexes |
| WO2019213894A1 (en) * | 2018-05-10 | 2019-11-14 | South University Of Science And Technology Of China | Alkynylplatinum (ii) terpyridine system coupled with rhodamine derivative: interplay of aggregation, de-aggregation and ring-opening processes for ratiometric luminescence sensing |
-
2022
- 2022-04-28 CN CN202210460402.4A patent/CN114773396B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030783A (en) * | 2009-09-30 | 2011-04-27 | 中国科学院理化技术研究所 | One-dimensional micron or submicron material of metal organic platinum (II) coordination compounds and preparation method and application |
| CN113896904A (en) * | 2021-11-16 | 2022-01-07 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
| CN114031646A (en) * | 2021-11-26 | 2022-02-11 | 昆明理工大学 | Cyclometalated platinum complex and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes;Ted M. Pappenfus et al.;《Inorganica Chimica Acta》;第1-2段、第2.7、2.9节 * |
| Glucose-Appended Platinum(II)-BODIPY Conjugates for Targeted Photodynamic Therapy in Red Light;Vanitha Ramu et al.;《Inorganic Chemistry》;Scheme S2 * |
| Ted M. Pappenfus et al..Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes.《Inorganica Chimica Acta》.2010,第1-2段、第2.7、2.9节. * |
| ZhengongMeng et al..NanoimprintLithography-DirectedSelf-AssemblyofBimetallic Iron–M(M=Palladium,Platinum)ComplexesforMagneticPatterning.《Angewandte Chemie》.2020,全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773396A (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109593105B (en) | Metal complex, organic electroluminescent device and organic electroluminescent material | |
| EP1904507A1 (en) | Metal complexes | |
| CN108409787B (en) | Phosphorescent manganese complex and preparation method and application thereof | |
| CN108129385B (en) | Composite quaternary ammonium salt nonlinear optical crystalline material and preparation method thereof | |
| CN114773396B (en) | Terpyridine platinum (II) complex and preparation method and application thereof | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN113354956B (en) | Near-infrared squaric acid dye connected with oxygen ether chain as well as preparation and application thereof | |
| CN113461545B (en) | Organic phosphorescence composition, preparation method and application thereof | |
| CN114874145A (en) | Water-soluble trityl free-based material and preparation method and application thereof | |
| CN115160588A (en) | Full-spectrum luminescent nanoscale zirconium-based metal organic framework material and preparation method thereof | |
| CN110981917B (en) | Amphiphilic double platinum complex and application thereof in preparation of luminescent nano assembly | |
| CN112250881A (en) | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material | |
| CN109320459B (en) | Fluorine-containing phenanthroimidazole derivative, crystal, preparation method and application thereof | |
| CN107118240B (en) | Method for improving luminous efficiency of europium complex | |
| CN111233753A (en) | Preparation method of AIE metal organogel | |
| CN111410646A (en) | 9, 10-dipyrrolyl anthracene fluorescent compound and preparation method and application thereof | |
| CN116144034B (en) | Metal triangle supermolecule with near infrared fluorescence, preparation method and application thereof | |
| CN114907416B (en) | Selenium-containing purple-refined coordination metal macrocyclic supermolecule, and synthesis method and application thereof | |
| CN115819281B (en) | Cyano-substituted p-phenylene ethylene derivative, preparation method and application | |
| CN109336894B (en) | Rigid conjugated macrocyclic compound with AIE effect and preparation and application thereof | |
| CN114478242B (en) | Salen-Ti complex catalyst and method for catalyzing asymmetric hydrogen atom transfer reaction by using same | |
| CN110964065B (en) | Fluorescence quencher based on cobalt metal complex, preparation method and application | |
| CN112538097B (en) | Metal organic complex, preparation method and application thereof | |
| CN109516985B (en) | 1, 3-di (2-pyridyl) benzene acceptor unit and indacenodipyridinedione organic semiconductor material and application | |
| CN117567519A (en) | Benzimidazole phosphine derivative ionic platinum (II) complex with excellent red light emission and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |