CN108148086A - Organic triplet photosensitizer with Host-guest Recognition group and preparation method thereof - Google Patents
Organic triplet photosensitizer with Host-guest Recognition group and preparation method thereof Download PDFInfo
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- CN108148086A CN108148086A CN201810077194.3A CN201810077194A CN108148086A CN 108148086 A CN108148086 A CN 108148086A CN 201810077194 A CN201810077194 A CN 201810077194A CN 108148086 A CN108148086 A CN 108148086A
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- dichloromethane
- triplet
- photosensitizer
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 202
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- -1 Hexamethylene diamine Chemical class 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 269
- 238000006243 chemical reaction Methods 0.000 claims description 127
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 70
- 239000002904 solvent Substances 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 51
- 238000004587 chromatography analysis Methods 0.000 claims description 49
- 238000000746 purification Methods 0.000 claims description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 36
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 35
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical class CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 claims description 17
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 238000010898 silica gel chromatography Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 108010077895 Sarcosine Proteins 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229940043230 sarcosine Drugs 0.000 claims description 15
- 235000010338 boric acid Nutrition 0.000 claims description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 14
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- 239000003480 eluent Substances 0.000 claims description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- 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 claims description 7
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229940087646 methanolamine Drugs 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 230000037361 pathway Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical group OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of organic triplet photosensitizers with Host-guest Recognition group and preparation method thereof, belong to photosensitizer synthesis technical field.The present invention passes through in C60Hexamethylene diamine is introduced in the organic triplet photosensitizer of Bodipy binary compounds on the middle position benzene ring position of Bodipy as supermolecule binding site, self assembly is carried out by the triplet photosensitizer with hyperon binding site and the supermolecule main block containing triplet receptor in the solution, in the range of space length to molecular dimension between the triplet that furthers photosensitizer and triplet receptor, so that triplet photosensitizer need not be spread in the range of useful life just can transmit energy, reduce the probability that triplet exciton is inactivated by non-radiative pathway, improve the energy transfer efficiency between photosensitizer and receptor, and then improve upper transfer efficiency.
Description
Technical field
The present invention relates to photosensitizer technical fields, and in particular to a kind of organic triplet light with Host-guest Recognition group
Quick dose and preparation method thereof.
Background technology
With the fast development of society, the worldwide energy shortage epoch quietly arrive, fossil fuel it is a large amount of
The mankind is driven increasingly to pay close attention to this inexhaustible safe environment protection type energy of solar energy using caused environmental problem
Source.The utilization ratio for improving solar energy is the unremitting pursuit of each subject scientist.
Upper switch technology is that energy photons can be changed into a technology of high-energy photons, is improving Solar use
Efficiency field has important value, has a wide range of applications in fields such as photovoltaic, photocatalysis, biological imagings at present.It is real
Now there are many upper method converted, such as upper convert can be achieved using rare earth metal, two-photon absorption dyestuff and mineral crystal.
Although conversion method has the characteristics of respective and special application field on these, there is also defects, such as rare earth
The absorbing ability of material is weaker, and operation wavelength is not easy to adjust, and upper conversion quantum efficiency is low etc.；Two-photon fluorescent dye (TPA) needs
The exciting light of high intensity is wanted, generally requires MW cm-2Rank is 10,000,000 times of sunlight intensity.These shortcomings cause these skills
Art is restricted in the application of the emerging fields such as solar cell.
Conversion (Triplet-triplet annihilation upconversion, letter on T-T annihilation
Claim TTA on convert), because its have needed for exciting light energy density small (sunlight can be used as excitation light source), photosensitizer to visible
The operation wavelength of strong, the upper conversion of absorbability of light can facilitate the advantages that adjustable and receive significant attention.Triplet excited state, TTA：
T-T annihilation (between acceptor molecule), 1A*：The singlet excited of receptor.The upper converting systems of TTA include two parts：
Triplet photosensitizer (energy donor) and triplet receptor (burying in oblivion agent) reach its excitation after triplet sensitiser absorption exciting light
Singlet state by intersystem crossing (ISC), reaches its excited triplet state；Photosensitizer molecule in excited triplet state is in photosensitizer
With acceptor molecule it is close when, the triplet of acceptor molecule is transferred energy to by collision, that is, triplet-triplet energies occur
It shifts (TTET), so as to which the triplet excited state for making acceptor molecule obtains population；Two acceptor molecules in triplet excited state touch
It hits, buries in oblivion, the singlet excited of an acceptor molecule is generated with certain probability, another then returns to ground state；In substance
The acceptor molecule of excitation state (S1) returns to ground state (S0) in the form of radiation transistion, sends out the fluorescence of conversion.
Triplet photosensitizer is mainly used as energy donor and causes new a photochemistry and photophysical process, such as sends out
Raw triplet-triplet energies transmission or electron transmission etc..Ideal triplet photosensitizer should have strong visible ray to inhale
Receipts ability, high ISC efficiency ensure that molecule has a higher triplet quantum yield, and the long triplet excited state service life is to ensure to have foot
The enough time occurs energy transmission, participates in the features such as various optical physics, photochemical reaction.Molecule triplet excited state obtains effective cloth
In electroluminescent, phosphorescent biological imaging or molecule sensing, photodynamic therapy, (PDT, sensitization generate the triplet photosensitizer of office
Singlet oxygen, 1O2), photocatalysis organic reaction, there is extensive use in the fields such as conversion on T-T annihilation.
Bury in oblivion in the introduction of upper switching mechanism from more than triplet as can be seen that triplet photosensitizer is conversion skill on such
The indispensable part of art, the photophysical property of triplet photosensitizer bury in oblivion triplet upper transfer efficiency and play important work
With.Up to the present, the triplet photosensitizer with supermolecule binding site has not been reported.With supermolecule binding site
Triplet photosensitizer buries in oblivion upper transfer efficiency with very important influence for improving triplet.
Bury in oblivion upper switching mechanism from triplet to learn, in generation conversion need two component parts-triplet photosensitizer with
Receptor collaboration is completed, and energy can be transmitted by needing to diffuse near receptor after the excitation of triplet photosensitizer light, this is in certain molecules
The defects of being very fatal in the system such as solid material of diffusion limited.
Invention content
The purpose of the present invention is to provide a kind of organic triplet photosensitizer with Host-guest Recognition group and its preparations
Method, to solve the problems, such as that existing photosensitizer transfer efficiency is low.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of organic triplet photosensitizer with Host-guest Recognition group, has the following structure：
Its molecular formula is：C102H57BF2N8O3S。
A kind of preparation method of organic triplet photosensitizer with Host-guest Recognition group, including：
(1) prepare compound F：
(11) compound B is synthesized using compound A and 1,2- Bromofume, wherein, compound A is parahydroxyben-zaldehyde,
The structure of compound B is：
(12) compound B is reacted in inert atmosphere with 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment,
After reaction, DDQ, triethylamine and BF are sequentially added3·OEt2The reaction was continued, and compound C is made, and the structure of compound C is：
(13) compound D is synthesized using compound C and N-iodosuccinimide, the structure of compound D is：
(14) compound D with 5- aldehyde radical -2- thienyl boric acids is mixed, then adds in K3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E, the structure of compound E is：
(15) compound E and NaN are utilized3Compound F is synthesized, the structure of compound F is：
(2) prepare compound c：
(21) 1,6- hexamethylene diamines and (BOC) are utilized2O synthesizes compound b, and the structure of compound b is：
(22) compound c is made using compound b and 3- propargyl bromide, the structure of compound c is：
(3) compound F made from step (1) with compound c made from step (2) is mixed, added in an inert atmosphere
CuSO4·5H2O and ascorbic acid reaction, are made compound G, the structure of compound G is：
(4) by compound G and C60It is mixed in inert atmosphere and reacts with sarcosine, organic triplet photosensitizer is made.
Further, in preferred embodiments of the present invention, prepare compound F includes process in detail below：
(11) hydroxy benzaldehyde is dissolved in ethyl alcohol, it is anti-at 75-80 DEG C then adds in 1,2- Bromofumes and potassium carbonate
7.5-8.5h is answered, after confirming that the reaction was complete using thin-layered chromatography, is filtered, compound B is made in purification；Wherein, hydroxy benzenes first
The molar ratio of aldehyde, glycol dibromide and potassium carbonate is 1:(4.8-5.5):(1.0-1.2), the expansion used in thin-layered chromatography
Agent is dichloromethane；
(12) in an inert atmosphere, compound B and dichloromethane are added in into reactor, while uses and vacuumizes displacement nitrogen
The mode of gas removes the oxygen of dissolving in methylene chloride, then adds in 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment
Middle reaction 8-12h；After confirming that the reaction was complete using thin-layered chromatography, DDQ stirrings are added in, react 0.8-1.5h postcooling reactants
System；Continue to add in triethylamine after stirring 10-20min, continue that BF is added dropwise after stirring 0.4-0.6h3·OEt2, carry after complete reaction
It is pure, compound C is made；Wherein, the molar ratio of compound B, 2,4- dimethyl pyrroles and DDQ are 1:2:1, triethylamine, BF3·
OEt2Molar ratio with compound B is 10:10:1, trifluoroacetic acid is catalytic amount, and the solvent used in thin-layered chromatography is two
Chloromethanes and n-hexane are according to 1:1 volume ratio mixes；
(13) compound C is dissolved in dichloromethane, under the conditions of ice-water bath, be added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 0.8-1.2h, and after confirming that the reaction was complete with thin-layered chromatography, compound D is made in purification；Its
In, the molar ratio of compound C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography is dichloromethane
With n-hexane according to 1:1 volume ratio mixes；
(14) compound D and 5- aldehyde radical -2- thienyl boric acids are dissolved in the in the mixed solvent that toluene and ethyl alcohol are formed, stirring is equal
K is added in after even3PO4·3H2O adds in catalyst Pd (OAc) in inert atmosphere2The back flow reaction 7.5-8.5h at 75-85 DEG C,
After confirming that the reaction was complete with thin-layered chromatography, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound
D, 5- aldehyde radicals -2- thienyl boric acids, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, it uses in thin-layered chromatography
Solvent be dichloromethane and n-hexane according to 1:1 volume ratio mixes；
(15) by NaN3It is dissolved in DMSO, compound E reaction 8-12min is then added dropwise, after complete reaction, purify, system
Obtain compound F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
It should be noted that in step (11), potassium carbonate is used for neutralization reaction product hydrogen bromide；In step (12),
Dichloromethane is not particularly limited as solvent, dosage, and " shading environment " can also be understood to be dark surrounds or dark
Case.
Further, in preferred embodiments of the present invention, in step (12), purification includes process in detail below：
The solvent in reaction product is removed, then further purified with silica gel chromatographic column with Rotary Evaporators, purification is obtained
A crude product cleaned with saturated sodium bicarbonate solution, then extracted with dichloromethane, merge organic layer, dried with sodium sulphate
Afterwards, it filters, obtained secondary crude product with silica gel column chromatography is purified, obtains compound C by concentration again；Wherein, silicagel column is adopted
Eluant, eluent is by dichloromethane：Petroleum ether is according to 1:1 volume ratio mixes.
Further, in preferred embodiments of the present invention, prepare compound c includes process in detail below：
(21) by (BOC)2O, which is dissolved in dichloromethane, to be mixed, after 2-3h, by mixed solution be added dropwise to ice-water bath 1,6- oneself
In diamines, 23-25h is reacted at room temperature, and after confirming that the reaction was complete with solvent, compound b is made in purification；Wherein, 1,6- oneself
Diamines and (BOC)2The molar ratio of O is (6-8):1 solvent is dichloromethane, methanol and triethylamine according to 100:10:1 volume
Than mixing；
(22) compound b and 3- propargyl bromide is dissolved in ethyl alcohol, then adds in K2CO3, it is heated to 35- under agitation
45 DEG C of reaction 2.5-3.5h, after confirming that the reaction was complete with solvent, compound c is made in purification；Wherein, compound b, 3- bromine third
Alkynes and K2CO3Molar ratio be 1:1:(2.5-3), solvent are dichloromethane and methanol according to 20:1 volume ratio mixing and
Into.
Further, in preferred embodiments of the present invention, step (3) includes process in detail below：
Compound F and compound c are dissolved in dichloromethane, add in CuSO under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming that the reaction was complete with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloro
Methane and methanol are according to 30:1 volume ratio mixes.
Further, in preferred embodiments of the present invention, step (4) includes process in detail below：
By compound G, C60After being mixed with sarcosine, toluene mixing is added in, mixed solution is warming up in an inert atmosphere
105-120 DEG C of back flow reaction 1.5-2.5h, is subsequently cooled to room temperature, and organic triplet photosensitizer is made in purification；Wherein, chemical combination
Object G, C60Molar ratio with sarcosine is 1:1:4.
In step (4), toluene is not particularly limited as solvent, dosage.The C that the present invention uses60Toluene solution,
Its concentration is preferably 1mg/ml.
Further, in preferred embodiments of the present invention, inert atmosphere is obtained by vacuumizing the method for displacement nitrogen.
The invention has the advantages that：
Organic triplet photosensitizer of the present invention with Host-guest Recognition site in chemical constitution, passes through the identification position
With being combined with the triplet receptor of supermolecule host-guest interaction occurs for point, and can further photosensitizer and receptor in diffusion limited system
Space length, so as to fulfill in diffusion limited system improve on transfer efficiency.
Organic triplet photosensitizer that the present invention synthesizes is the noval chemical compound do not reported, with Host-guest Recognition group：
The middle position benzene ring position of Bodipy reacts introducing one end by Click and hexamethylene diamine is protected to be used as supermolecule combination by tertbutyloxycarbonyl
The purpose of one end amido protecting is to improve the stability of photosensitizer by site, tertbutyloxycarbonyl, is preserved convenient for it, the protection
Group can remove in acid condition, and acid condition can make protonated amino simultaneously, and hexamethylene diamine and cucurbit after protonating
[6] urea has strong host-guest interaction, Formation constants>108M.Such photosensitizer is with having modified the three of aforementioned body molecule
When weight state receptor combines, the energy transfer efficiency between triplet photosensitizer and triplet receptor can be improved, and then improve three
Weight state triplet buries in oblivion the efficiency of upper conversion.
Organic triplet photosensitizer of the present invention passes through in C60In the organic triplet photosensitizer of-Bodipy binary compounds
Hexamethylene diamine is introduced on the middle position benzene ring position of Bodipy as supermolecule binding site, the position is to the light object of triplet photosensitizer
Rationality matter does not influence, and passes through the triplet photosensitizer with hyperon binding site and the supermolecule master containing triplet receptor
Body carries out self assembly in the solution, the space length between the triplet that furthers photosensitizer and triplet receptor to molecular dimension range
It is interior so that have bigger molecule size contains C60Organic triplet photosensitizer need not spread in the range of useful life and just can pass
Pass energy, so as to reduce the probability that triplet exciton is inactivated by non-radiative pathway, improve triplet photosensitizer and triplet by
Energy transfer efficiency between body, and then improve upper transfer efficiency.
The present invention, by building the reaction environment being protected from light, is avoided in the step when synthesizing key intermediate compound C
One of raw material used：2,4- dimethyl pyrroles light or oxygen and situation apt to deteriorate and yield is caused to reduce；And
The rate of charge of stringent control compound B and 2,4- dimethyl pyrrole of the invention is 1:2；Under the stringent control of two conditions,
So that the yield of compound C is obviously improved.In addition, in subsequent purification step, the present invention is washed with saturated sodium bicarbonate water,
So as to it is remaining after reacting with chromatographic column be difficult that the boron trifluoride ether that separates is removed by acid-base neutralization, improving
The product purity of object C is closed, so as to improve compound C integral product quality, base is laid subsequently to synthesize organic triplet photosensitizer
Plinth provides guarantee for final product quality.
Description of the drawings
Fig. 1 is the synthetic route chart of compound F；
Fig. 2 is the synthetic route chart of compound c；
Fig. 3 is organic triplet photosensitizer：The synthetic route chart of compound H；
Fig. 4 is the nmr spectrum chart of compound C；
Fig. 5 is the nmr spectrum chart of compound D；
Fig. 6 is the nmr spectrum chart of compound E；
Fig. 7 is the nmr spectrum chart of compound F；
Fig. 8 is the nmr spectrum chart of compound b；
Fig. 9 is the nmr spectrum chart of compound c；
Figure 10 is the nmr spectrum chart of compound d；
Figure 11 is organic triplet photosensitizer：The nmr spectrum chart of compound H.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.The person that is not specified actual conditions in embodiment, the item suggested according to normal condition or manufacturer
Part carries out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, including：
(1) prepare compound F：
Synthetic route is as shown in Figure 1.
(11) compound A and glycol dibromide synthesis compound B are utilized.Detailed process is as follows：
Hydroxy benzaldehyde is dissolved in ethyl alcohol, then adds in the reaction 8h of 1,2- Bromofumes and potassium carbonate at 78 DEG C, profit
It after confirming that the reaction was complete with thin-layered chromatography, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,2- Bromofumes
Molar ratio with potassium carbonate is 1:5:1, the solvent used in thin-layered chromatography is dichloromethane.The specific mistake of this step purification
Cheng Wei：Reaction product is extracted with dichloromethane, merges organic phase, uses anhydrous Na2SO4It is dry and organic with Rotary Evaporators removing
Obtained crude product is purified (eluant, eluent by solvent with silica gel column chromatography：Dichloromethane).
The yield of compound B is 30.4%.
(12) compound B is reacted in inert atmosphere with 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment,
After reaction, DDQ, triethylamine and BF are successively added in3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows：
In an inert atmosphere, compound B and dry methylene chloride are added in into reactor, while uses and vacuumizes displacement nitrogen
The mode of gas removes the oxygen of dissolving in methylene chloride, then adds in 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment
Middle reaction 10h；After confirming that the reaction was complete using thin-layered chromatography, DDQ stirrings are added in, react 1h postcooling reaction systems；Continue
Triethylamine is added in after stirring 15min, continues that BF is added dropwise after stirring 0.5h3·OEt2, it purifies after complete reaction, it is apparent when having
After fluorescence-causing substance point generates, show that the reaction was complete, compound C is made；Wherein, compound B, 2,4- dimethyl pyrroles and DDQ
Molar ratio is 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, trifluoroacetic acid is catalytic amount, thin layer
The solvent used in chromatography is dichloromethane and n-hexane according to 1:1 volume ratio mixes.The purification of this step includes
Process in detail below：The solvent in reaction product is removed, then further purified with silica gel chromatographic column with Rotary Evaporators, will purified
An obtained crude product is cleaned with saturated sodium bicarbonate solution, is then extracted with dichloromethane, is merged organic layer, is used sodium sulphate
It after drying, filters, obtained secondary crude product with silica gel column chromatography is purified, obtains compound C by concentration again；Wherein, silica gel
The eluant, eluent that column uses is dichloromethane：Petroleum ether is according to 1:What 1 volume ratio mixed.
Compound C is orange-yellow, yield 11.4%.
(13) compound C and N-iodosuccinimide synthesis compound D are utilized.Detailed process is as follows：
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 1h, and after confirming that the reaction was complete with thin-layered chromatography, compound D is made in purification；Wherein, chemical combination
The molar ratio of object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography is dichloromethane and n-hexane
According to 1:1 volume ratio mixes.The purification of this step includes process in detail below：Reaction product is removed with Rotary Evaporators
Organic solvent, by obtained crude product silica gel column chromatography separating-purifying.
Compound D is orange-yellow, yield 55.9%.
(14) compound D with 5- aldehyde radical -2- thienyl boric acids is mixed, then adds in K3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesis compound E.Detailed process is as follows：
Compound D and 5- aldehyde radical -2- thienyl boric acids are dissolved in the in the mixed solvent that toluene and ethyl alcohol are formed, after stirring evenly
Add in K3PO4·3H2O adds in catalyst Pd (OAc) in inert atmosphere2Back flow reaction 8h, uses thin-layered chromatography at 80 DEG C
After confirming that the reaction was complete, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2- thiophenes
Fen boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the solvent used in thin-layered chromatography is two
Chloromethanes and n-hexane are according to 1:1 volume ratio mixes.The purification of this step includes process in detail below：It will be obtained by the reaction
Crude product purified by silica gel column chromatography purifies, and eluant, eluent is dichloromethane：N-hexane=1:1.
Compound E be red powder, yield 14.2%.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows：
By NaN3It is dissolved in DMSO, compound E reaction 10min is then added dropwise, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.The purification of this step includes process in detail below：Determine that raw material is basic
After having reacted, at once plus water is washed, and milkiness shape occurs in solution at this time, then adds in suitable NaCl and goes to emulsify, then uses CH2Cl2
Extraction, collected organic layer Na2SO4It after drying, is spin-dried for, crude product silica gel column chromatography separating-purifying.
Compound F be red product, yield 85.4%.
(2) prepare compound c：
Synthetic route is as shown in Figure 2.
(21) 1,6- hexamethylene diamines and (BOC) are utilized2O synthesis compounds b.Detailed process is as follows：
By (BOC)2O, which is dissolved in dichloromethane, to be mixed, and after 2-3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamines of ice-water bath
In, it reacts at room temperature for 24 hours, after confirming that the reaction was complete with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamines with
(BOC)2The molar ratio of O is 7.7:1, solvent is dichloromethane, methanol and triethylamine according to 100:10:1 volume ratio mixing
It forms.The purification of this step includes process in detail below：Suitable quantity of water is added in into product and washes away unreacted 1,6- hexamethylene diamines, mistake
Filter, filtrate use CH2Cl2Extraction, organic layer Na2SO4After drying, solvent is removed with Rotary Evaporators, slightly uses product rubber column gel column color
(eluant, eluent is dichloromethane for spectrum purification：Methanol：Triethylamine=100:10:1) it, is developed the color with ninhydrin.
Compound b be colourless liquid, yield 17.9%.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows：
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, then adds in K2CO3, it is heated to 40 DEG C of reactions under agitation
3h, after confirming that the reaction was complete with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3Rub
You are than being 1:1:2.8, solvent is dichloromethane and methanol according to 20:1 volume ratio mixes.This step purification include with
Lower detailed process：The organic solvent in product is removed with Rotary Evaporators, the separation of obtained crude product silica gel column chromatography is carried
Pure (washing and dehydrating integrated machine CH2Cl2：CH3OH=20：1).
Compound c is yield 26.6%.
(3) prepare compound G：
Synthetic route is as shown in Figure 3.
Compound F and compound c are dissolved in dichloromethane, add in CuSO under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming that the reaction was complete with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloro
Methane methanol is according to 30:1 volume ratio mixes.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After being mixed with sarcosine, toluene mixing is added in, mixed solution is warming up in an inert atmosphere
110 DEG C of back flow reaction 2h, are subsequently cooled to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60And flesh
The molar ratio of propylhomoserin is 1:1:4.The purification of this step includes process in detail below：It is gone out product solvent with Rotary Evaporators, it is thick to produce
Product are purified with silica gel column chromatography, and eluant, eluent is toluene:N-hexane=5:1.
Red product H is organic triplet photosensitizer.
Embodiment 2
The present embodiment is slightly different with reaction condition of the embodiment 1 difference lies in each step, specific as follows：
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, including：
(1) prepare compound F：
(11) compound A and glycol dibromide synthesis compound B are utilized.Detailed process is as follows：
Hydroxy benzaldehyde is dissolved in ethyl alcohol, then adds in the reaction 7.5h of 1,2- Bromofumes and potassium carbonate at 75 DEG C,
It after confirming that the reaction was complete using thin-layered chromatography, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,2- dibromo second
The molar ratio of alkane and potassium carbonate is 1:4.8:1, the solvent used in thin-layered chromatography is dichloromethane.
(12) compound B is reacted in inert atmosphere with 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment,
After reaction, DDQ, triethylamine and BF are successively added in3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows：
In an inert atmosphere, compound B and dry methylene chloride are added in into reactor, while uses and vacuumizes displacement nitrogen
The mode of gas removes the oxygen of dissolving in methylene chloride, then adds in 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment
Middle reaction 8h；After confirming that the reaction was complete using thin-layered chromatography, DDQ stirrings are added in, react 0.8h postcooling reaction systems；Continue
Triethylamine is added in after stirring 10min, continues that BF is added dropwise after stirring 0.4h3·OEt2, it purifies after complete reaction, it is apparent when having
After fluorescence-causing substance point generates, show that the reaction was complete, compound C is made；Wherein, compound B, 2,4- dimethyl pyrroles and DDQ
Molar ratio is 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, trifluoroacetic acid is catalytic amount, thin layer
The solvent used in chromatography is dichloromethane and n-hexane according to 1:1 volume ratio mixes.
(13) compound C and N-iodosuccinimide synthesis compound D are utilized.Detailed process is as follows：
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 0.8h, and after confirming that the reaction was complete with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for dichloromethane and just oneself
Alkane is according to 1:1 volume ratio mixes.
(14) compound D with 5- aldehyde radical -2- thienyl boric acids is mixed, then adds in K3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesis compound E.Detailed process is as follows：
Compound D and 5- aldehyde radical -2- thienyl boric acids are dissolved in the in the mixed solvent that toluene and ethyl alcohol are formed, after stirring evenly
Add in K3PO4·3H2O adds in catalyst Pd (OAc) in inert atmosphere2Back flow reaction 7.5h, uses thin-layer chromatography at 75 DEG C
After method confirms that the reaction was complete, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2-
Thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the solvent used in thin-layered chromatography for
Dichloromethane and n-hexane are according to 1:1 volume ratio mixes.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows：
By NaN3It is dissolved in DMSO, compound E reaction 8min is then added dropwise, after complete reaction, compound is made in purification
F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
(2) prepare compound c：
(21) 1,6- hexamethylene diamines and (BOC) are utilized2O synthesis compounds b.Detailed process is as follows：
By (BOC)2O, which is dissolved in dichloromethane, to be mixed, and after 2h, mixed solution is added dropwise to 1, the 6- hexamethylene diamines of ice-water bath
In, 23h is reacted at room temperature, and after confirming that the reaction was complete with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamines with
(BOC)2The molar ratio of O is 6:1 solvent is dichloromethane, methanol and triethylamine according to 100:10:1 volume ratio mixing and
Into.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows：
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, then adds in K2CO3, it is heated to 35 DEG C of reactions under agitation
2.5h, after confirming that the reaction was complete with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3's
Molar ratio is 1:1:2.5, solvent is dichloromethane and methanol according to 20:1 volume ratio mixes.
(3) prepare compound G：
Compound F and compound c are dissolved in dichloromethane, add in CuSO under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming that the reaction was complete with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloro
Methane methanol is according to 30:1 volume ratio mixes.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After being mixed with sarcosine, toluene mixing is added in, mixed solution is warming up in an inert atmosphere
105 DEG C of back flow reaction 1.5h, are subsequently cooled to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60With
The molar ratio of sarcosine is 1:1:4.
Embodiment 3
The present embodiment is slightly different with reaction condition of the embodiment 1 difference lies in each step, specific as follows：
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, including：
(1) prepare compound F：
(11) compound A and glycol dibromide synthesis compound B are utilized.Detailed process is as follows：
Hydroxy benzaldehyde is dissolved in ethyl alcohol, then adds in the reaction 8.5h of 1,2- Bromofumes and potassium carbonate at 80 DEG C,
It after confirming that the reaction was complete using thin-layered chromatography dichloromethane, filters, compound B is made in purification；Wherein, hydroxy benzaldehyde, 1,
The molar ratio of 2- Bromofumes and potassium carbonate is 1:5.5:1.2, the solvent used in thin-layered chromatography is dichloromethane.
(12) compound B is reacted in inert atmosphere with 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment,
After reaction, DDQ, triethylamine and BF are successively added in3·OEt2The reaction was continued, and compound C is made.Detailed process is as follows：
In an inert atmosphere, compound B and dry methylene chloride are added in into reactor, while uses and vacuumizes displacement nitrogen
The mode of gas removes the oxygen of dissolving in methylene chloride, then adds in 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment
Middle reaction 12h；After confirming that the reaction was complete using thin-layered chromatography, DDQ stirrings are added in, react 1.5h postcooling reaction systems；After
Triethylamine is added in after continuous stirring 20min, continues that BF is added dropwise after stirring 0.6h3·OEt2, it purifies after complete reaction, it is apparent when having
Fluorescence-causing substance point generate after, show that the reaction was complete, compound C be made；Wherein, compound B, 2,4- dimethyl pyrroles and DDQ
Molar ratio be 1:2:1, triethylamine, BF3·OEt2Molar ratio with compound B is 10:10:1, trifluoroacetic acid is catalytic amount, thin
The solvent used in layer chromatography is dichloromethane and n-hexane according to 1:1 volume ratio mixes.
(13) compound C and N-iodosuccinimide synthesis compound D are utilized.Detailed process is as follows：
Compound C is dissolved in dry methylene chloride, under the conditions of ice-water bath, is added dropwise dissolved with N-iodosuccinimide
Dry methylene chloride solution reacts 1.2h, and after confirming that the reaction was complete with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for dichloromethane and just oneself
Alkane is according to 1:1 volume ratio mixes.
(14) compound D with 5- aldehyde radical -2- thienyl boric acids is mixed, then adds in K3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesis compound E.Detailed process is as follows：
Compound D and 5- aldehyde radical -2- thienyl boric acids are dissolved in the in the mixed solvent that toluene and ethyl alcohol are formed, after stirring evenly
Add in K3PO4·3H2O adds in catalyst Pd (OAc) in inert atmosphere2Back flow reaction 8.5h, uses thin-layer chromatography at 85 DEG C
After method confirms that the reaction was complete, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5- aldehyde radical -2-
Thienyl boric acid, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2：0.05, the solvent used in thin-layered chromatography for
Dichloromethane and n-hexane are according to 1:1 volume ratio mixes.
(15) compound E and NaN are utilized3Synthesize compound F.Detailed process is as follows：
By NaN3It is dissolved in DMSO, compound E reaction 12min is then added dropwise, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
(2) prepare compound c：
(21) 1,6- hexamethylene diamines and (BOC) are utilized2O synthesis compounds b.Detailed process is as follows：
By (BOC)2O, which is dissolved in dichloromethane, to be mixed, and after 3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamines of ice-water bath
In, 25h is reacted at room temperature, and after confirming that the reaction was complete with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamines with
(BOC)2The molar ratio of O is 8:1 solvent is dichloromethane, methanol and triethylamine according to 100:10:1 volume ratio mixing and
Into.
(22) compound c is made using compound b and 3- propargyl bromide.Detailed process is as follows：
Compound b and 3- propargyl bromide is dissolved in ethyl alcohol, then adds in K2CO3, it is heated to 45 DEG C of reactions under agitation
3.5h, after confirming that the reaction was complete with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide and K2CO3's
Molar ratio is 1:1:3, solvent is dichloromethane and methanol according to 20:1 volume ratio mixes.
(3) prepare compound G：
Compound F and compound c are dissolved in dichloromethane, add in CuSO under an inert atmosphere4·5H2O and ascorbic acid
Reaction after confirming that the reaction was complete with thin-layered chromatography, is taken out product and is refrigerated, compound G is made；Wherein, compound F, chemical combination
Object c, CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloro
Methane and methanol are according to 30:1 volume ratio mixes.
(4) compound G and C60It is reacted with sarcosine
By compound G, C60After being mixed with sarcosine, toluene mixing is added in, mixed solution is warming up in an inert atmosphere
120 DEG C of back flow reaction 2.5h, are subsequently cooled to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G, C60With
The molar ratio of sarcosine is 1:1:4.
Embodiment 4
The preparation method of organic triplet photosensitizer with Host-guest Recognition group of the present embodiment, including：
1. the synthesis of compound B
Parahydroxyben-zaldehyde (6.0g, 49.2mmol) is dissolved in 60mL ethyl alcohol in three-necked flask, adds in 1,2- bis-
Bromoethane (46.2g, 21.0mL, 246.0mmol) and potassium carbonate (6.6g, 47.0mmol) heat 78 DEG C instead after being sufficiently stirred
Should, about react 8 hours.After TCL (dichloromethane is solvent) confirms that parahydroxyben-zaldehyde fundamental reaction is complete, filtering, so
It is extracted afterwards with dichloromethane, merges organic phase, use anhydrous Na2SO4Drying simultaneously removes organic solvent with Rotary Evaporators, obtains
Crude product purifies (eluant, eluent with silica gel column chromatography：Dichloromethane), obtain product B (3.4g).Yield：30.4%.
2. the synthesis of compound C
The oxygen in reaction system is removed with the method for vacuumizing displacement nitrogen, adds in compound B under nitrogen protection
In (2.3g, 10.0mmol) to three-necked flask, the dichloromethane that 400.0mL is dried with molecular sieve is added, then vacuumize displacement
The method of nitrogen removes the oxygen dissolved in dichloromethane, fully takes 2,4- dimethyl pyrroles with 5mL syringes after removing oxygen
(2.2mL, 20.0mmol) is injected into reaction bulb, then trifluoroacetic acid 0.2mL is added in same method again, in rubber stopper
Vacuum grease is coated at pin hole, reaction system, which is then encased shading, with masking foil reacts an evening.TCL (solvents：Dichloromethane
Alkane) confirm that raw material adds in DDQ (2.3g, 10.0mmol) after react, stirring 1 hour, then with ice-water bath cooling reaction system,
Lower addition 12mL triethylamines after stirring 15 minutes, continue to stir 0.5h, then 12.0mL BF are added dropwise with dropper3·OEt2, after
Continuous reaction a period of time, stopping is anti-after confirmation reaction intermediate raw material has almost reacted and had apparent fluorescence-causing substance point
Should, it is slightly purified with silica gel column chromatography after then removing a part of solvent with Rotary Evaporators, removes a large amount of impurity, then obtaining
Crude product saturation NaHCO3It is extracted after solution washing with dichloromethane, merges organic layer, use Na2SO4After drying, filtering is dense
Contracting, crude product are purified with silica gel column chromatography, and eluant, eluent is (dichloromethane：Petroleum ether=1：1) orange product C, is obtained
(510.0mg), yield 11.4%.
Compound C：1HNMR(400MHz,CDCl3):7.20 (d, 2H, J=8.64Hz), 7.04 (d, 2H, J=
8.62Hz), 6.00 (s, 2H), 4.38 (t, 2H, J=6.21Hz), 3.71 (t, 2H, J=6.23Hz), 2.57 (s, 6H), 1.45
(s,6H).
3. the synthesis of compound D
Compound C (200.0mg, 44.6mmol) is dissolved in the CH of 30mL molecular sieves drying2Cl2In, ice-water bath condition
Under, with constant pressure funnel the 50mL molecular sieves for being dissolved with N-iodosuccinimide (NIS) (100.4mg, 44.6mmol)
Dry CH2Cl2Solution is slowly added dropwise in compound C solution, and about 1h is added dropwise to complete, a reaction was continued hour, Ran Houyong
(solvent is dichloromethane to TCL：N-hexane=1:1) confirm raw material after the reaction was complete.Organic solvent is removed with Rotary Evaporators,
Crude product silica gel column chromatography separating-purifying obtains orange product D (143.0mg), yield：55.9%.
Compound D:1HNMR(400MHz,CDCl3):7.19 (d, 2H, J=8.65Hz), 7.05 (d, 2H, J=
8.66Hz), 6.07 (s, 1H), 4.39 (t, 2H, J=6.22Hz), 3.72 (t, 2H, J=6.25Hz), 2.65 (s, 3H), 2.59
(s,H),1.46(s,6H).
4. the synthesis of compound E
5- aldehyde radical -2- thienyl boric acids (228.7mg, 1.5mmol) and intermediate D (251.9mg, 0.5mmol) are dissolved in
The in the mixed solvent of 10mL toluene and 10mL ethyl alcohol, K is added in after being sufficiently stirred3PO4·3H2O (260mg, 1.0mmol), then makes
With the deoxidation method for vacuumize-replacing nitrogen, it is catalyzed being added in after the oxygen in this operation circulation 3~5 times fully system of going out
Agent Pd (OAc)2(6.4mg, 0.03mmol), then mixed liquor be heated to 80 DEG C of back flow reactions 8 hours, (solvent is dichloro to TCL
Methane：N-hexane=1:1) after determining that raw material fundamental reaction is complete, stop reaction, be cooled to room temperature, crude product purified by silica gel column chromatography
Purification, eluant, eluent is dichloromethane：N-hexane=1:1, obtain red powder product (544.0mg), yield：14.2%.
Compound E:1HNMR(400MHz,CDCl3):9.87 (s, 1H), 7.73 (d, 1H, J=3.54), 7.20 (d, 2H, J
=8.05Hz), 7.04 (d, 2H, J=8.02Hz), 6.94 (d, 1H, J=3.51Hz), 6.07 (s, 1H), 4.36 (t, 2H, J=
6.16Hz), 3.69 (t, 2H, J=6.11Hz), 2.59 (d, 6H, J=8.16Hz), 1.46 (s, 6H)
5. the synthesis of compound F
By NaN3(15.2mg, 0.2mmol) is dissolved in 10mL DMSO, be then added dropwise to intermediate E (44.0mg,
Reaction about 10min or so in 0.08mmol), after determining that raw material fundamental reaction is complete, at once plus there is milkiness shape in water washing, solution,
It adds in suitable NaCl to go to emulsify, then uses CH2Cl2Extraction, collected organic layer Na2SO4It after drying, is spin-dried for, crude product silicon
Rubber column gel column chromatographic purification.Finally obtain red product F (34.6mg), yield：85.4%.
Compound F:1HNMR(400MHz,CDCl3):9.89 (s, 1H), 7.75 (d, 1H, J=3.85Hz), 7.23 (d,
2H, J=8.61Hz), 7.08 (d, 2H, J=8.62Hz), 6.97 (d, 1H, J=3.83Hz), 6.10 (s, 1H), 4.24 (t, 2H,
), J=5.03Hz 3.69 (t, 2H, J=4.91Hz), 2.62 (d, 6H, J=8.28Hz), 1.48 (d, 6H, J=2.02Hz)
6. the synthesis of compound b
By (BOC)2O (1.0g, 4.6mmol) is dissolved in 12mL CH2Cl2It is middle about 2.5h be added dropwise to ice-water bath 1,6- oneself
In diamines (4.1g, 35.6mmol), then react at room temperature for 24 hours, (solvent is dichloromethane to TCL：Methanol：Triethylamine=
100:10:1) it after determining reaction raw materials a reactions to a certain extent, then adds in suitable quantity of water and washes away unreacted 1,6- hexamethylene diamines,
Filtering, filtrate use CH2Cl2Extraction, organic layer Na2SO4After drying, solvent is removed with Rotary Evaporators, slightly uses product rubber column gel column
(eluant, eluent is dichloromethane to chromatography purity：Methanol：Triethylamine=100:10:1) it, is developed the color with ninhydrin.Separating-purifying obtains nothing
Color liquid b (1.4g), yield 17.9%.
Compound b:1HNMR(400MHz,CDCl3):4.59 (s, 1H), 3.10 (d, 2H, J=6.08Hz), 2.70 (t,
2H, J=7.01Hz), 2.11 (s, 2H), 1.48-1.44 (m, 3H), 1.39-1.28 (m, 4H)
7. the synthesis of compound c, d
Intermediate b (1.3g, 6.4mmol) and 3- propargyl bromides (0.8g, 6.4mmol) by 1:1 equivalent is dissolved in 20mL
Ethyl alcohol in, while add in K2CO3(2.5g,18.2mmol).It is heated to 40 DEG C under conditions of stirring to react 3 hours, TCL (exhibitions
Agent is opened as dichloromethane：Methanol=20:1) confirm that raw material stops reaction after the reaction was complete, removed with Rotary Evaporators organic molten
Agent, crude product is with silica gel column chromatography separating-purifying (washing and dehydrating integrated machine CH2Cl2：CH3OH=20：1) it, collects and obtains bilateral product d
(274.0mg), yield：33.1%；Obtain unilateral product c (200.0mg), yield：26.6%.
8. the synthesis of compound G
By intermediate product F (34.6mg, 0.07mmol) and intermediate product c (16.0mg, 0.07mmol) by 1：1 equivalent is molten
Solution is in the CH of 6mL2Cl2In, it then vacuumizes-replaces nitrogen and remove oxygen, add in CuSO under nitrogen protection4·5H2O(5mg)
With ascorbic acid (8mg).Solvent is (CH2Cl2：MeOH=30:1), determine that raw material stops reaction after having reacted, at room temperature
Contact plate is spin-dried for determine to be dissolved in CH after product G is purer2Cl2Middle placement refrigerator preserves for use (due to product less stable, easily become
Matter is so fail to weigh up quality)
9. the synthesis of compound H
By above-mentioned intermediate product G (0.05mmol), C60(37.7mmol, 0.05mmol) and sarcosine (16.2mg,
It 0.2mmol) is added in bis- mouthfuls of bottles of 100mL, is adding in 35mL toluene, then vacuumizing-replace nitrogen three times, protected in nitrogen
Under, mixed liquor is to slowly warm up to 110 DEG C, then back flow reaction 2h is down to room temperature, is gone out solvent with Rotary Evaporators, crude product
It is purified with silica gel column chromatography, eluant, eluent is toluene:N-hexane=5:1.Obtain red product H.
Fig. 4 to Figure 11 is the nmr spectrum chart of compound that above-described embodiment 4 is synthesized in each step, according to collection of illustrative plates
Determine the chemical constitution of each compound.
Compound H prepared by the present invention intends being used as triplet photosensitizer, and the triplet receptor with being connected with supermolecule is led
Object interact, so as to fulfill in diffusion limited system realize triplet bury in oblivion on convert.Organic triplet of the present invention
Photosensitizer in use, carry out acidification at room temperature by it with trifluoroacetic acid, then again with being connected with the triplet of supermolecule
Receptor combines.Excessive trifluoroacetic acid is removed by Rotary Evaporators after acidification.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of organic triplet photosensitizer with Host-guest Recognition group, has the following structure：
。
2. the preparation method of organic triplet photosensitizer described in claim 1 with Host-guest Recognition group, feature exist
In, including：
(1) prepare compound F：
(11) compound B is synthesized using compound A and 1,2- Bromofume, wherein, the compound A is parahydroxyben-zaldehyde,
The structure of the compound B is：
(12) the compound B is reacted in inert atmosphere with 2,4- dimethyl pyrroles and trifluoroacetic acid in shading environment,
After reaction, DDQ, triethylamine and BF are sequentially added3·OEt2The reaction was continued, and compound C, the structure of the compound C is made
For：
(13) using the compound C and N-iodosuccinimide synthesis compound D, the structure of the compound D is：
(14) the compound D with 5- aldehyde radical -2- thienyl boric acids is mixed, then adds in K3PO4·3H2O, then in indifferent gas
At catalyst Pd (OAc) in atmosphere2Under the action of synthesize compound E, the structure of the compound E is：
(15) the compound E and NaN is utilized3Compound F is synthesized, the structure of the compound F is：
(2) prepare compound c：
(21) 1,6- hexamethylene diamines and (BOC) are utilized2O synthesizes compound b, and the structure of the compound b is：
(22) compound c is made using the compound b and 3- propargyl bromides, the structure of the compound c is：
(3) compound F described made from step (1) is mixed with the compound c made from step (2), in an inert atmosphere
Add in CuSO4·5H2O and ascorbic acid reaction, are made compound G, the structure of the compound G is：
(4) by the compound G and C60It is mixed in inert atmosphere and reacts with sarcosine, organic triplet photosensitizer is made.
3. the preparation method of organic triplet photosensitizer according to claim 2 with Host-guest Recognition group, special
Sign is that prepare compound F includes process in detail below：
(11) hydroxy benzaldehyde is dissolved in ethyl alcohol, then adds in the reaction of 1,2- Bromofumes and potassium carbonate at 75-80 DEG C
7.5-8.5h, after confirming that the reaction was complete using thin-layered chromatography, is filtered, and compound B is made in purification；Wherein, hydroxy benzaldehyde,
The molar ratio of glycol dibromide and potassium carbonate is 1:(4.8-5.5):(1.0-1.2), the solvent used in thin-layered chromatography
For dichloromethane；
(12) in an inert atmosphere, compound B and dichloromethane are added in into reactor, while nitrogen is replaced using vacuumizing
Mode removes the oxygen of dissolving in methylene chloride, and it is anti-in shading environment then to add in 2,4- dimethyl pyrroles and trifluoroacetic acid
Answer 8-12h；After confirming that the reaction was complete using thin-layered chromatography, DDQ stirrings are added in, react 0.8-1.5h postcooling reaction systems；
Continue to add in triethylamine after stirring 10-20min, continue that BF is added dropwise after stirring 0.4-0.6h3·OEt2, it purifies after complete reaction,
Compound C is made；Wherein, the molar ratio of compound B, 2,4- dimethyl pyrroles and DDQ are 1:2:1, triethylamine, BF3·OEt2With
The molar ratio of compound B is 10:10:1, trifluoroacetic acid is catalytic amount, and the solvent used in thin-layered chromatography is dichloromethane
With n-hexane according to 1:1 volume ratio mixes；
(13) compound C is dissolved in dichloromethane, under the conditions of ice-water bath, the drying dissolved with N-iodosuccinimide is added dropwise
Dichloromethane solution reacts 0.8-1.2h, and after confirming that the reaction was complete with thin-layered chromatography, compound D is made in purification；Wherein, change
The molar ratio for closing object C and N-iodosuccinimide is 1:1, the solvent used in thin-layered chromatography for dichloromethane and just oneself
Alkane is according to 1:1 volume ratio mixes；
(14) compound D and 5- aldehyde radical -2- thienyl boric acids are dissolved in the in the mixed solvent that toluene and ethyl alcohol are formed, after stirring evenly
Add in K3PO4·3H2O adds in catalyst Pd (OAc) in inert atmosphere2Back flow reaction 7.5-8.5h, use are thin at 75-85 DEG C
After layer chromatography confirms that the reaction was complete, stop heating, be cooled to room temperature, compound E is made after purification；Wherein, compound D, 5-
Aldehyde radical -2- thienyl boric acids, K3PO4·3H2O and Pd (OAc)2Molar ratio be 1:3:2:0.05, the exhibition used in thin-layered chromatography
It is dichloromethane and n-hexane according to 1 to open agent:1 volume ratio mixes；
(15) by NaN3It is dissolved in DMSO, compound E reaction 8-12min is then added dropwise, after complete reaction, chemical combination is made in purification
Object F；Wherein, compound F and NaN3Molar ratio be 0.4:1.
4. the preparation method of organic triplet photosensitizer according to claim 3 with Host-guest Recognition group, special
Sign is, in step (12), purification includes process in detail below：
The solvent in reaction product is removed, then further purified with silica gel chromatographic column with Rotary Evaporators, one that purification is obtained
Secondary crude product is cleaned with saturated sodium bicarbonate solution, is then extracted with dichloromethane, merges organic layer, after being dried with sodium sulphate,
Filtering, concentration, obtained secondary crude product with silica gel column chromatography is purified again, obtains compound C；Wherein, silicagel column uses
Eluant, eluent by dichloromethane：Petroleum ether is according to 1：1 volume ratio mixes.
5. the preparation method of organic triplet photosensitizer according to claim 2 with Host-guest Recognition group, special
Sign is that prepare compound c includes process in detail below：
(21) by (BOC)2O, which is dissolved in dichloromethane, to be mixed, and after 2-3h, mixed solution is added dropwise to 1, the 6- hexamethylene diamines of ice-water bath
In, 23-25h is reacted at room temperature, and after confirming that the reaction was complete with solvent, compound b is made in purification；Wherein, 1,6- hexamethylene diamines
With (BOC)2The molar ratio of O is (6-8):1 solvent is dichloromethane, methanol and triethylamine according to 100:10:1 volume ratio is mixed
It closes；
(22) compound b and 3- propargyl bromide is dissolved in ethyl alcohol, then adds in K2CO3, it is heated to 35-45 DEG C under agitation
2.5-3.5h is reacted, after confirming that the reaction was complete with solvent, compound c is made in purification；Wherein, compound b, 3- propargyl bromide with
And K2CO3Molar ratio be 1:1:(2.5-3), solvent are dichloromethane and methanol according to 20:1 volume ratio mixes.
6. according to the preparation side of organic triplet photosensitizer of the claim 2-5 any one of them with Host-guest Recognition group
Method, which is characterized in that step (3) includes process in detail below：
Compound F and compound c are dissolved in dichloromethane, add in CuSO under an inert atmosphere4·5H2O and ascorbic acid are anti-
Should, after confirming that the reaction was complete with thin-layered chromatography, take out product and refrigerate, compound G is made；Wherein, compound F, compound
c、CuSO4·5H2The molar ratio of O and ascorbic acid is 1:1:0.3:0.6, the solvent used in thin-layered chromatography is dichloromethane
Alkane and methanol are according to 30:1 volume ratio mixes.
7. the preparation method of organic triplet photosensitizer according to claim 6 with Host-guest Recognition group, special
Sign is that step (4) includes process in detail below：
By compound G, C60After being mixed with sarcosine, toluene mixing is added in, mixed solution is warming up to 105- in an inert atmosphere
120 DEG C of back flow reaction 1.5-2.5h, are subsequently cooled to room temperature, and organic triplet photosensitizer is made in purification；Wherein, compound G,
C60Molar ratio with sarcosine is 1:1:4.
8. the preparation method of organic triplet photosensitizer according to claim 7 with Host-guest Recognition group, special
Sign is that the inert atmosphere is obtained by vacuumizing the method for displacement nitrogen.
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