CN106800575A - 宽谱带可见光吸收三重态光敏剂及其制法和用途 - Google Patents
宽谱带可见光吸收三重态光敏剂及其制法和用途 Download PDFInfo
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- CN106800575A CN106800575A CN201611244646.XA CN201611244646A CN106800575A CN 106800575 A CN106800575 A CN 106800575A CN 201611244646 A CN201611244646 A CN 201611244646A CN 106800575 A CN106800575 A CN 106800575A
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- Prior art keywords
- sensitising agent
- broad band
- triplet
- solvent
- pyrroles
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- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 40
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010948 rhodium Substances 0.000 claims abstract description 15
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 11
- AMZABBNNBJXIGP-UHFFFAOYSA-N [B].[F].N1C=CC=CC=C1.C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] Chemical compound [B].[F].N1C=CC=CC=C1.C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] AMZABBNNBJXIGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 229940126062 Compound A Drugs 0.000 claims description 14
- 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 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- DTKVAHYKYRDBSY-UHFFFAOYSA-N [B].[F].N1C=CC=CC=C1 Chemical compound [B].[F].N1C=CC=CC=C1 DTKVAHYKYRDBSY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 benzylidene chalcones Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- YBCUEJCLNHHXBS-UHFFFAOYSA-K [Rh](Cl)(Cl)Cl.C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2 Chemical compound [Rh](Cl)(Cl)Cl.C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2 YBCUEJCLNHHXBS-UHFFFAOYSA-K 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000008359 benzonitriles Chemical class 0.000 claims description 3
- 235000005513 chalcones Nutrition 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012453 solvate Substances 0.000 claims description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 3
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 238000006552 photochemical reaction Methods 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 238000000862 absorption spectrum Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000002165 resonance energy transfer Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 231100000489 sensitizer Toxicity 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 30
- 230000009102 absorption Effects 0.000 description 23
- 229940106691 bisphenol a Drugs 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 230000005284 excitation Effects 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004497 NIR spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SBHDJEBOAUTUSH-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Rh] SBHDJEBOAUTUSH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002280 anti-androgenic effect Effects 0.000 description 1
- 239000000051 antiandrogen Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
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- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy 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
- C07F15/0073—Rhodium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
Abstract
一种基于宽谱带可见光吸收三重态光敏剂，它有如下结构：
Description
技术领域
本发明涉及宽谱带可见光吸收三重态光敏剂材料，具体地说，涉及铑四苯基卟啉-氮杂氟硼二吡咯{Rh(ttp)-aza-BODIPY}宽谱带可见光吸收三重态光敏剂及其制法和用途。
背景技术
双酚A(Bisphenol,BPA)是一类重要的工业原料，广泛地用于合成聚碳酸酯、环氧树脂、聚苯醚树脂等高分子材料。然而，双酚A具有弱雌激素活性和强抗雄激素活性，是一种典型的内分泌激素干扰物，微量的摄取将对人体健康造成威胁。[参见：(a)毛茂乔，单国强，夏佳慧，等.水热法合成BiOI及在模拟太阳光下对双酚A的降解.科学通报，2014,59,3072-3079；(b)Wu,W.；Shan,G.Q.；Wang,S.F.,et al.Environmentally relevant impacts ofnano-TiO2 on abiotic degradation of bisphenol A under sunlightirradiation.Environ.Pollut.,2016,216,166-172.]全球每年双酚A生产价值超过80亿英镑，如此大量的应用使得双酚A广泛存在于天然水体中和饮用水中，因此其降解技术日益受到关注。
双酚A的处理方法主要是光催化氧化方法。[参见：(a)Wu,W.；Shan,G.Q.；Wang,S.F.,et al.Environmentally relevant impacts of nano-TiO2 on abioticdegradation of bisphenol A under sunlight irradiation.Environ.Pollut.,2016,216,166-172；(b)Murgolo,S.；Petronella,F.；Ciannarella,R.,et al.Catal.Today2015,240,114-124；(c)Yan,T.；Liu,H.；Sun,M.,et al.RSC Adv.2015,5,10688-10696.]然而，目前这些处理方法仍然存在着一些不足之处，难以达到理想的处理效果。如光催化氧化方法通常情况下需要使用高能的紫外光源，然而这部分紫外光仅占太阳光光谱的不到5％,导致高成本以及繁琐的处理过程。为了高效利用太阳光中丰富的可见光，染料敏化光降解方法吸引了很多研究者关注。[参见：(a)Bower,J.P.；Anastasio,C.Environ.Sci.:Processes Impacts,2014,16,748-756；(b)Escalada,J.P.；Pajares,A.；Gianotti,J.etal.Chemosphere 2006,65,237-244；c)Kim,H.；Kim,W.；Mackeyev,Y.,etal.Environ.Sci.Technol.,2012,46,9606-9613；(d)Liu,N.；Sun,G.Ind.Eng.Chem.Res.,2011,50,5326-5333]此方法只需要氧气，适当波长的光源以及能够吸收光能并将能量传递给周围氧气分子的三重态光敏剂。[参见：Thandu,M.；Comuzzi,C.；Goi,D.Int.J.Photoenergy 2015,1-22]它的主要过程是：光敏剂在光照情况下，电子吸收能量从基态跃迁到单重激发态，单重激发态一部分电子回到基态时发射荧光，另外一部分电子通过系间窜越过程从单重激发态跃迁到三重激发态，三重激发态将能量传递给周围的氧气分子，从而产生单线态氧，由于单线态氧具有非常强的氧化性，可以将有机污染物转化成生物可降解的化合物。通常情况下，三重态光敏剂在可见光区只有一个吸收带。然而，在光降解反应中，通常使用宽谱带光源，如太阳光、氙灯等，这样会导致光敏剂不能有效地利用激发光源的能量。但是，宽谱带强可见光吸收三重态光敏剂的合成却鲜有报道，在有机污染物降解方面的应用研究更是从未报道。因此，为了提高光能利用效率，设计合成在可见光区具有宽波段强吸收和单线态氧高效产生于一体的三重态光敏剂，并将其用于降解有机污染物具有重要的意义。
发明内容
在本发明中，我们巧妙地将铑卟啉和aza-BODIPY通过金属-碳键直接相连。在这种连接方式中，过渡金属d轨道直接参与前线分子轨道成键，由于重金属d轨道的参与,系间窜越系数显著增加，从而有效地产生单线态氧。同时，该合成设计将两个在可见光区不同位置具有强吸收的荧光分子有机结合起来，得到宽谱带可见光吸收三重态光敏剂，该设计合成不受共振能量转移诸多因素的制约，而且合成步骤简便。所合成的三重态光敏剂吸收光谱覆盖范围从380nm-750nm，无论采用其吸收光谱中任何波长激发都可以高效地产生单线氧，因此所得到的光敏剂可以高效地利用复合光源的能量，如太阳光，氙灯等，其更有利于广泛的应用。这是一种非常简单灵活的方法，可以根据需要通过改变过渡金属配合物或者改变与其相连的荧光分子获得一系列宽谱带可见光吸收的三重态材料，这为我们提供一种新颖简便的合成方法。
本发明内容是设计并提供了一类铑卟啉-氮杂氟硼二吡咯{Rh(ttp)-aza-BODIPY}宽谱带可见光吸收三重态光敏剂材料及其制备方法和用途研究。
本发明涉及技术方案如下：
一种基于铑卟啉-氮杂氟硼二吡咯的宽谱带可见光吸收三重态光敏剂，它有如下结构：
一种制备上述基于铑卟啉-氮杂氟硼二吡咯宽谱带可见光吸收三重态光敏剂的方法，它包括下列步骤：：
(1)aza-BODIPY-a的合成
4-甲氧基-苯乙酮(1eq)和4-溴-苯甲醛(1eq)加入10mL乙醇溶剂中，缓慢滴加10％NaOH水溶液(2.5eq)，反应5小时结束，减压抽滤，水洗至中性，少量冷乙醇洗，抽干得黄色产品1a苯亚甲基查尔酮；取1a(1eq)于50mL圆底烧瓶中，硝基甲烷(5eq)和乙二胺(5eq)，30mL甲醇溶剂，65℃回流12小时，反应结束后反应混合物用蒸馏水和乙酸乙酯萃取，用无水硫酸钠干燥有机层，减压旋蒸除去溶剂，干燥得到产物2a.取2a(1eq)于50mL两颈圆底烧瓶中，加入乙酸铵(5eq)，氮气保护下于30mL正丁醇中加热回流24h，反应结束冷却至室温，过滤，用冷乙醇洗涤，干燥得到深蓝色固体3a；50mL两颈烧瓶中，加入3a(1eq)，10mL重蒸二氯甲烷溶液，三乙胺(20eq)和(20eq)三氟化硼乙醚溶液，氮气保护下室温反应24小时，反应混合物用蒸馏水、饱和食盐水依次洗涤，然后无水硫酸钠干燥，减压浓缩，用100-140目硅胶装柱分离，用CH2Cl2/hexane(1:1v/v)的展开剂进行硅胶柱层析分离，得到目标化合物aza-BODIPY-a。
其反应式如下：
(2)RhIII(ttp)Cl的合成
在100mL圆底烧瓶中加入四苯基卟啉H2(ttp)(1eq),三水氯化铑RhCl3·3H2O(2eq)和15mL苯甲腈回流72小时，待反应结束，减压旋干溶剂，用CH2Cl2的展开剂进行硅胶柱层析分离，得到目标产物。其反应式如下：
(3)A的合成
在反应器中加入铑四苯基卟啉氯化物(Rh(ttp)Cl)(1eq)、卤代氮杂氟硼二吡咯(aza-BODIPY-a)(1.1eq)、K2CO3(20eq)和苯溶剂，反应混合物冷冻脱气三次，在氮气保护下150℃反应，待反应结束，减压旋干溶剂，用CH2Cl2/hexane的展开剂进行硅胶柱层析分离，得到基于铑卟啉-氮杂氟硼二吡咯的宽谱带可见光吸收的化合物A。
用1H-NMR、UV-Vis、Fluorescence spectral、MALDI-TOF MASS表征并证实了该光敏剂的结构(见附图1-4)。
紫外光谱表明我们所合成的目标化合物吸收光谱范围宽，摩尔吸光系数大，这样有利用高效地吸收太阳光。从三维荧光光谱看出，发射波长与激发波长无关，表明化合物A是单一的荧光分子。
另外，以亚甲蓝做参比,波长671nm的单色激光器为光源测试了目标化合物的稳定性和单线态氧的效率值，并采用不同激发波长检测单线态氧近红外发射光谱。实验结果表明所合成的目标化合物具有良好的光稳定性，而且无论采用吸收光谱中任何波长激发都可以有效地产生单线态氧，而单线态氧可以用于光解有机污染物。我们在黑暗和太阳光照条件下分别进行了光敏剂A太阳光降解双酚A的测试。实验结果表明在无光照射条件下，随着时间的延长，双酚A的浓度几乎不发生变化，维持在100％左右。相比之下，在太阳光照射下，双酚A的浓度随着光照时间的延长显著降低，表明光敏剂A有很强的光降解能力。
本发明的有益效果
本发明与现有技术相比，其显著优点是：通过Rh-C键轴向连接方式合成了铑卟啉-氮杂氟硼二吡咯{Rh(ttp)-aza-BODIPY}化合物。此化合物兼具有过渡金属铑和aza-BODIPY的光学性质。一方面，由于中心金属RhШ独特的d6电子构型，使得该化合物具有强的系间窜越系数，高效地产生单线态氧。另一方面，该合成设计将在可见光区不同位置具有强吸收的荧光分子有机结合起来，可以成功得到宽谱带、强可见光吸收、且能够高效产生单线态氧的三重态光敏剂。这些研究成果为我们提供一种更简便灵活的制备宽谱带可见光吸收三重态光敏剂的方法。与传统的合成宽谱带可见光吸收三重态光敏剂方法相比，我们的合成方法不受共振能量转移诸多因素的制约，具有简便灵活的优点。另外，所得到的光敏剂与传统的单色团荧光材料相比，本发明中所合成的化合物具备高效利用太阳光能量，同时可以有效的产生单线态氧等优点，而单线态氧能够将有机污染物转化成可降解的化合物，同时还可以杀死细菌，真菌和病毒。因此，我们所得到的光敏剂可以用于太阳光光解有机污染物。另外，单线态氧可以和多种有机化合物反应，如各类烯烃、硫醚、酚类化合物以及富电子的芳香化合物等，是一种非常有价值的氧化剂，因此该光敏剂还可以用于太阳光催化有机反应。
附图说明
图1为本发明中光敏剂A的核磁氢谱图；
图2为本发明中光敏剂A的质谱图；
图3为本发明中光敏剂A的紫外吸收光谱；
图4为本发明中光敏剂A的三维荧光光谱图；
图5为本发明中光敏剂A与亚甲基蓝单线态氧产生效率对比图；
图6为本发明中光敏剂A在不同激发波长单线态氧近红外发射光谱图；
图7为本发明中光敏剂A的稳定性图；
图8为本发明中在光敏剂A作用下太阳光降解双酚A结果。
具体实施方式
检测所用仪器为：BrukerARX500型核磁共振仪(TMS为内标，氘代C6D6为溶剂)，岛津UV-4500型紫外－可见分光光度计(扫描范围300-900nm,狭缝宽度2.0nm)，日立F-4600美国BrukerDaltonicsautoflexII质谱工作站。
实施例1.化合物A的合成
化合物aza-BODIPY-a按文献方法制备(Gorman,A.；Killoran,J.；O'Shea,C.F.,etal.In vitro demonstration of the heavy-atom effect for photodynamictherapy.J.Am.Chem.Soc.2004,126,10619-10631)，具体合成方法如下：
在100mL圆底烧瓶中，加入(10mmol)的4-甲氧基-苯乙酮和(10mmol)的4-溴-苯甲醛于10mL乙醇溶剂中，缓慢滴加(10mL)10％NaOH水溶液，反应5小时结束，减压抽滤，水洗至中性，少量冷乙醇洗，抽干得黄色产品1a苯亚甲基查尔酮；取(4mmol)1a于50mL圆底烧瓶中，20mmol硝基甲烷和20mmol乙二胺，30mL甲醇溶剂，65℃回流12小时，反应结束后反应混合物用蒸馏水和乙酸乙酯萃取，无水硫酸钠干燥，合并有机层减压、抽滤、干燥得到产物2a.取(3mmol)2a于50mL两颈圆底烧瓶中，加入75mmol乙酸铵，氮气保护下于30mL正丁醇中加热回流24h，反应结束冷却至室温，过滤，用冷乙醇洗涤，干燥得到深蓝色固体3a；50mL两颈烧瓶中，加入(0.15mmol)3a，10mL重蒸二氯甲烷溶液，3mmol三乙胺和3mmol三氟化硼乙醚溶液，氮气保护下室温反应24小时，反应混合物用蒸馏水、饱和食盐水依次洗涤，然后无水硫酸钠干燥，减压浓缩，用CH2Cl2/hexane(1:1)的展开剂进行硅胶柱层析分离(100-140目，青岛海洋化工厂)，得到目标化合物aza-BODIPY-a.1H NMR(500MHz,CDCl3):δ3.89(s,6H),7.01(d,J＝9.0Hz,4H),7.02(s,2H),7.59(d,J＝8.5Hz,4H),7.90(d,J＝8.5Hz,4H),8.07(d,J＝9.0Hz,4H).MALDI-TOF MS:m/z:713.13.
化合物Rh(ttp)Cl按照文献合成(Chan,K.S.；Lau,C.M.Syntheses of acylporphyrins by aldehydic carbon-hydrogen bond activation with Rh(Ⅲ)porphyrinchloride and methyl.Organometallics,2006,25,260-265)，具体合成方法如下：
在100mL圆底烧瓶中加入四苯基卟啉H2(ttp)(100mg,0.149mmol),三水氯化铑RhCl3·3H2O(79mg,0.298mmol)和15mL苯甲腈回流72小时。待反应结束，减压旋干溶剂，用CH2Cl2的展开剂进行硅胶柱层析分离，得到72mg产物。产率：60％.Rf＝0.12(CH2Cl2/hexane＝1:1).1H NMR(400MHz,CDCl3):δ2.70(s,2H),8.07(d,J＝7.5Hz,8H),8.20(m,8H),8.93(m,8H).MALDI-TOF MS:807.175.
化合物A的合成，具体合成方法如下：
在反应器中加入铑四苯基卟啉氯化物Rh(ttp)Cl(15.8mg,0.019mmol)，氮杂氟硼二吡咯aza-BODIPY-a(13.7mg,0.021mmol)，K2CO3(53.9mg,0.39mmol)和1.0mL苯，反应混合物冷冻脱气三次，在氮气保护下150℃反应28小时。待反应结束，减压旋干溶剂，用CH2Cl2/hexane(1:1)的展开剂进行硅胶柱层析分离，得到17.1mg化合物A.产率：61％.Rf＝0.61(CH2Cl2/hexane ＝1:1).1H NMR(400MHz,CDCl3):δ0.44(d,J＝8.5Hz,2H),2.69(s,12H),5.45(d,J＝8.4Hz,2H),5.98(s,1H),6.75(s,1H),7.30-7.36(m,6H),7.45(d,J＝8.0Hz,2H),7.51-7.52(m,9H),7.56-7.63(m,3H),7.80(d,J＝3.3Hz,2H),8.04(d,J＝7.7Hz,4H),8.09(d,J＝7.8Hz,4H),8.87(s,8H)；13C NMR(175MHz,CDCl3):δ21.60,117.08,117.54,123.05,123.77,124.31,124.64,127.49,127.66,128.35,128.38,129.22,129.29,129.97,130.29,130.86,131.02,131.14,131.59,131.69,131.93,133.92,134.22,137.42,138.90,140.04,143.05,143.97,145.44,145.55,156.83,160.71.MALDI-TOF MS:m/z:Calcd for[C82H60BBrF2RhN7O2]+([M]+)：1405.3108，Found:1406.555[M]+,1387.556[M-F]+,1429.358[M+Na]+,1445.322[M+K]+。
实施例2.应用
将目标化合物A溶解在甲苯溶剂中配置成5×10-5mol/L溶液，采用紫外和荧光光谱法测定A的紫外吸收光谱和三维荧光光谱(如图3-4所示)。紫外光谱表明我们所合成的目标化合物A吸收光谱范围宽，摩尔吸光系数大，这样有利于高效地吸收太阳光。从三维荧光光谱看出，发射波长与激发波长无关，表明化合物A是单一的荧光分子。
在二氯甲烷溶剂中，以亚甲基蓝为参比(亚甲基蓝在二氯甲烷中的单线态氧效率值为0.57)，1,3-二苯基苯并呋喃(DPBF)为捕获剂，波长671nm的单色激光器为光源测试目标化合物A的单线态氧效率。具体测试过程：首先将光敏剂A与DPBF溶液混合，调整A的浓度使其在激发波长处吸收控制在0.2左右，然后用671nm的激光照射一定的时间，光敏剂A经激光照射后会产生单线态氧，产生的单线态氧与DPBF发生反应生成无色的产物，由于DPBF本身有颜色，在411nm处有强吸收，因此单线态氧的产生会使411nm处的吸收降低，然后测试411nm处吸收值随照射时间变化，绘制411nm处吸收降级值与激光照射时间线性关系图，得到曲线斜率，如图5所示，结果表明化合物A可以有效地产生单线态氧，其单线态氧效率为0.33。同时采用405nm和690nm激发波长检测单线态氧近红外发射光谱。实验结果表明两个激发波长都可以有效地产生单线态氧，采用激发光谱能量校正，根据单线态氧发射光谱积分面积得到两个波长处单线态氧效率比值，结果表明不同激发波长处单线态氧效率值一致，这说明光敏剂A无论采用吸收波长中任何激发波长激发都可以有效地产生单线态氧。
以亚甲基蓝为参比，测定A的光稳定性。具体测试过程：采用671nm激光器为激发光源，照射化合物A，每照射3min测定一次吸收光谱，连续照射1h，研究激发波长处吸收光谱强度随激光照射时间变化，从而得到目标化合物的光稳定性。实验结果表明所合成的目标化合物A随着激发时间的延长，吸收光谱几乎不发生变化，从而说明化合物A相对于亚甲基蓝来讲具有更好的光稳定性(如图6所示)。
单线态氧具有很强的反应活性，可以用于光解有机污染物。具体测试过程：将化合物A和双酚A分别配置成1×10-5mol/L和1×10-4mol/L，溶剂为CH2Cl2/CH3CH2OH(1/9)，取1.5mL A和1.5mL双酚A置于密封的四面通光比色皿中，充分混匀后分别在黑暗和太阳光照条件下进行光敏剂A太阳光降解双酚A的测试。双酚A在280nm波长处有强吸收，因此可采用吸收光谱监控双酚A降解情况。在黑暗条件下，随着时间的延长，双酚A的浓度几乎不发生变化，维持在100％左右。相比之下，在太阳光照射下，最初间隔10min测定一次吸光度，20min后每隔20min测定一次，结果表明双酚A的吸收随着光照时间的延长显著降低，表明光敏剂A有很强的光降解能力。其双酚A降解测试结果见图8。
Claims (4)
1.一种基于铑卟啉-氮杂氟硼二吡咯宽谱带可见光吸收三重态光敏剂，其特征是它有如下结构：
2.一种制备权利要求1所述的基于铑卟啉-氮杂氟硼二吡咯宽谱带可见光吸收三重态光敏剂的方法，它包括下列步骤：
(1)aza-BODIPY-a的合成
取1eq的4-甲氧基-苯乙酮和1eq的4-溴-苯甲醛加入10mL乙醇溶剂中，缓慢滴加2.5eq的10％NaOH水溶液()，反应5小时结束，减压抽滤，水洗至中性，冷乙醇洗涤，抽干得黄色产品1a苯亚甲基查尔酮；取1eq的1a于50mL圆底烧瓶中，加入5eq的硝基甲烷、5eq的乙二胺和30mL甲醇溶剂，65℃回流12小时，反应结束后反应混合物用蒸馏水和乙酸乙酯萃取，用无水硫酸钠干燥有机层，减压旋蒸除去溶剂，干燥得到产物2a.取1eq的2a于50mL两颈圆底烧瓶中，加入5eq的乙酸铵，氮气保护下于30mL正丁醇中加热回流24h，反应结束冷却至室温，过滤，用冷乙醇洗涤，干燥得到深蓝色固体3a；在50mL两颈烧瓶中，加入1eq的3a，10mL重蒸二氯甲烷溶液，20eq的三乙胺和20eq三氟化硼乙醚溶液，氮气保护下室温反应24小时，反应混合物用蒸馏水、饱和食盐水依次洗涤，然后无水硫酸钠干燥，减压浓缩，用100-140目硅胶装柱分离，用CH2Cl2/hexane(1:1v/v)的展开剂进行硅胶柱层析分离，得到目标化合物aza-BODIPY-a；
(2)RhIII(ttp)Cl的合成
在100mL圆底烧瓶中加入四苯基卟啉H2(ttp)(1eq),三水氯化铑RhCl3·3H2O(2eq)和15mL苯甲腈回流72小时，待反应结束，减压旋干溶剂，用CH2Cl2的展开剂进行硅胶柱层析分离，得到目标产物；
(3)A的合成
在反应器中加入铑四苯基卟啉氯化物(Rh(ttp)Cl)(1eq)、卤代氮杂氟硼二吡咯(aza-BODIPY-a)(1.1eq)、K2CO3(20eq)和苯溶剂，反应混合物冷冻脱气三次，在氮气保护下150℃反应，待反应结束，减压旋干溶剂，用CH2Cl2/hexane的展开剂进行硅胶柱层析分离，得到基于铑卟啉-氮杂氟硼二吡咯的宽谱带可见光吸收的化合物A。
3.权利要求1所述的基于铑卟啉-氮杂氟硼二吡咯宽谱带可见光吸收三重态光敏剂，作为光敏剂在光化学反应中的应用。
4.根据权利要求3所述的基于铑卟啉-氮杂氟硼二吡咯宽谱带可见光吸收三重态光敏剂，在光降解有机污染物双酚A中的应用。
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