CN106221280A - Novel organic dye sensitizer containing BODIPY conjugated units and preparation method thereof - Google Patents
Novel organic dye sensitizer containing BODIPY conjugated units and preparation method thereof Download PDFInfo
- Publication number
- CN106221280A CN106221280A CN201610648381.3A CN201610648381A CN106221280A CN 106221280 A CN106221280 A CN 106221280A CN 201610648381 A CN201610648381 A CN 201610648381A CN 106221280 A CN106221280 A CN 106221280A
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- China
- Prior art keywords
- reaction
- organic dye
- bodipy
- preparation
- under
- Prior art date
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- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 62
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- -1 alkoxyl iodobenzene Chemical compound 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 3
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 3
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 238000006887 Ullmann reaction Methods 0.000 claims description 2
- 238000010751 Ullmann type reaction Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- APFVFJFRJDLVQX-AHCXROLUSA-N indium-111 Chemical compound [111In] APFVFJFRJDLVQX-AHCXROLUSA-N 0.000 claims description 2
- 229940055742 indium-111 Drugs 0.000 claims description 2
- 150000003235 pyrrolidines Chemical class 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 2
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 208000035126 Facies Diseases 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000003480 eluent Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 0 N*(*1C2=CC=C1)(*1=CC=CC1=C2c(cc1)ccc1O)N Chemical compound N*(*1C2=CC=C1)(*1=CC=CC1=C2c(cc1)ccc1O)N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- ZKHZWXLOSIGIGZ-UHFFFAOYSA-N 5-methoxy-11h-benzo[b][1]benzazepine Chemical compound COC1=CC2=CC=CC=C2NC2=CC=CC=C12 ZKHZWXLOSIGIGZ-UHFFFAOYSA-N 0.000 description 1
- IWCBFNUUALXQBB-UHFFFAOYSA-N B(O)(O)O.B(F)(F)F Chemical compound B(O)(O)O.B(F)(F)F IWCBFNUUALXQBB-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000013742 energy transducer activity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
-
- 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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a novel organic dye sensitizer containing BODIPY and a preparation method thereof. The organic dye sensitizer is an organic photosensitive dye with a D-pi-A structure, meso-substituted BODIPY nuclear bridged phenyl is used as a pi bridge skeleton, triphenylamine derivatives are used as electron donor units, and cyanoacetic acid is used as an electron acceptor unit. The invention also discloses a preparation method of the organic dye sensitizer, molecules of the organic dye sensitizer are prepared by two-step Suzuki coupling reaction and one-step Knoevenagel condensation reaction, and the structural general formula is shown as I. The organic dye sensitizer has simple molecular synthesis method, easy control, high yield and the likeThe method has universal applicability, and can be applied to the preparation of dye-sensitized solar cells to obtain dye-sensitized solar cell materials with excellent performance.
Description
Technical field:
The present invention relates to dyestuff quick China solar cell material field, be specifically related to a kind of novel containing BODIPY class conjugation
Organic dye sensitized dose of unit.
Background technology:
From Switzerland in 1991Group uses bipyridyl ruthenium as dyestuff and nanoporous TiO first2Film preparation
Since DSSC (DSSCs), dye sensitized nano crystal TiO2Solaode is just by low preparation cost
Higher photoelectric transformation efficiency becomes recent two decades and carrys out the study hotspot in solar energy photoelectric conversion field.BODIPY parent nucleus has
Multiple avtive spots, can carry out suitable modification and functionalization according to calorifics, optically and electrically performance requirement.People are by right
Each site of BODIPY parent nucleus is modified, and has synthesized the novel B ODIPY dyestuff of many excellent performances.Researchers generally select
Select and modify on two pyrrole rings of BODIPY parent, by introducing the functional group of different performance, can effective extension body
System's conjugation chain length, increases the rigid planar structure of core, and wherein at the 3 of parent nucleus, 5-position and 2,6-introduces substituent group on position
The spectrum property of dye molecule is affected maximum.2,6-modifies position to the BODIPY dye sensitizing agent of receptor electron group 2012
Year is the reports such as Dai, and they have synthesized with BODIPY for conjugated pi bridge, and benzimidizole derivatives is donor monomer, and cyanoacetic acid is for inhaling
A series of dyestuffs of attached group.The wider absorption spectrum of such molecule displays, energy conversion efficiency has been up to 2.26%,
This is high-photoelectric transformation efficiency based on BODIPY dye-sensitized cell device at that time, presents huge application potential.So
And, about this kind of 2, the efficiency of the BODIPY dye sensitizing agent that 6-position is modified is not significantly improved always.
Triphenylamine is the electron transport material that another kind of photoelectric properties are excellent, owing to it has strong electron donation and former
Expect cheap being easy to get, be the most increasingly widely used in DSSC field.But its nonplanar stereochemical structure reduces light
Absorption, therefore BODIPY unit is combined by we with the triphenylamine derivative of different rigidity, it is desirable to improve dyestuff to light
Absorption and light capture rate, thus improve the performance of battery.By changing the rigid planar structure of donor, the different donor of research
The electron donation size of the unit spectrum to dyestuff and the regulating and controlling effect of energy level, thus improve battery performance parameter.
Summary of the invention:
It is an object of the invention to provide a kind of novel containing organic dye sensitized dose of BODIPY class conjugate unit, there is novelty
Molecular structure, having relatively low edge energy, wide spectral absorption scope, and its preparation method is simple, synthetic ratio is high.
It is a further object to provide this preparation method containing organic dye sensitized dose of BODIPY class conjugate unit,
Its preparation method is simple, and purifying products is simple, and productivity is high, and has universality.
For achieving the above object, the present invention is by the following technical solutions:
A kind of novel containing BODIPY conjugate unit organic dye sensitized dose, this material has a chemical constitution of logical formula (I):
In formula (I), D is donor monomer, the one in following construction unit:
Wherein, R, R1For H or CnH2n+1Alkyl or alkoxyl, n is the natural number of 1-20.
The preparation method of a kind of novel containing BODIPY conjugate unit organic dye sensitized dose, comprises the following steps:
(1) under the effect of alkali, hydroxy benzaldehyde, through alkylated reaction, prepares intermediate 1, and its structure is:
(2) intermediate 1 and pyrroles are condensed to yield two pyrrolidine intermediate, two pyrrolidines under triethylamine effect with borontrifluoride
Borate ether complex reaction obtains intermediate 2, and its structure is:
(3) intermediate 2 and iodine monochloride are through electrophilic substitution reaction, prepare intermediate 3, and its structure is:
(4) intermediate 3 under the effect of four (triphenylphosphinyl) palladium with 4-formylphenylboronic acid through Suzuki coupling reaction,
Preparing intermediate 4, its structure is:
(5) intermediate 4 again with iodine monochloride through electrophilic substitution reaction, prepare intermediate 5, its structure is:
(6) to alkoxyl iodobenzene and para-bromoaniline through ullmann reaction, obtaining intermediate 6, its structure is:
(7) intermediate 6 is through Suzuki coupling reaction under the catalytic action of four (triphenylphosphinyl) palladium, prepares intermediate 7,
Its structure is:
(8) 10-Alkoximino stilbene with to bromo-iodobenzene through Buchwald Hartwig coupling reaction, obtain intermediate 8,
Its structure is:
(9) intermediate 8 is through Suzuki coupling reaction under the catalytic action of four (triphenylphosphinyl) palladium, obtains intermediate 9,
Its structure is:
(10) will to alkoxyl iodobenzene and 2-bromine carbazole under Hydro-Giene (Water Science). is catalyzed through Liv Ullmann condensation reaction, in preparing
Mesosome 10, its structure is:
(11) by intermediate 10 with duplex pinacol boron ester through Suziki coupling reaction, prepare intermediate 11, its structure
For:
(12) intermediate 7, intermediate 9 and intermediate 11 respectively with intermediate 5 through Suzuki coupling reaction, prepare intermediate
12,13,14, its structure is:
D is
(13) intermediate 12,13,14 respectively under the effect of cyanoacetic acid through Knoevenagel condensation reaction, prepare respectively
Target dyestuff Dye1,2,3, its structure is:
Preferred as technique scheme, in step (1)-(13), the reaction medium of described reaction is acetonitrile, N, N-bis-
One or more in methylformamide, methanol, oxolane, dichloromethane, 1,4-dioxane, toluene, chloroform, ethanol are mixed
Close.
Preferred as technique scheme, described in step (2), (6), (8), (11), (12) and (13) in reaction, institute
Catalyst be Indium-111 chloride, four (triphenylphosphinyl) palladium, three (dibenzalacetone) two palladium, Cu-lyt., Hydro-Giene (Water Science).
With the one in piperidines.
Preferred as technique scheme, step (1), (4), (6), (7), (8), (9), (10), (11), (12) and
(13), in described reaction, alkali used is in potassium carbonate, triethylamine, potassium hydroxide, potassium acetate, piperidines and sodium tert-butoxide
Kind.
Preferred as technique scheme, in step (1)-(13), the reaction temperature in described reaction is 25-120 DEG C,
Response time is 2-48h.
The method have the advantages that
(1) in synthetic method, the method raw material is commonly easy to get, and production cost is low, and reaction condition is more easy to control.
(2) by the spectral data analysis to dyestuff, we can see that such dyestuff has good photon capture energy
Power, has wide uv absorption scope compared to the dyestuff of document report, is applied to DSSC, has high
Photoelectric transformation efficiency.
Accompanying drawing illustrates:
Fig. 1 is Dye 1-3 ultra-violet absorption spectrum in dichloromethane solution；
Fig. 2 is that Dye1-3 is at TiO2Normalized uv-visible absorption spectra on film；
Fig. 3 is the nucleus magnetic hydrogen spectrum of Dye 1；
Fig. 4 is the nuclear-magnetism carbon spectrum of Dye 1；
Fig. 5 is the nucleus magnetic hydrogen spectrum of Dye 2；
Fig. 6 is the nuclear-magnetism carbon spectrum of Dye 2；
Fig. 7 is the nucleus magnetic hydrogen spectrum of Dye 3；
Fig. 8 is the nuclear-magnetism carbon spectrum of Dye 3；
Fig. 9 is Dye 1-3 cyclic voltammetry curve in dichloromethane solution；
Figure 10 is the I-V curve that Dye 1-3 prepares organic dye sensitized solaode.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, the present invention will not be constituted any restriction.
(1) synthesis of intermediate 1
The round-bottomed flask of 500mL is sequentially added into hydroxy benzaldehyde (12.5g, 0.1mol), potassium carbonate (16.5g,
0.12mol), n-octane bromide (23.2g, 0.12mol) and 150mL acetonitrile, magnetic agitation, reaction temperature is controlled at 80 DEG C anti-
Answer 10h.Stopped reaction, is removed by filtration solid residue with suction funnel, is spin-dried for solvent, by dchloromethane, massive laundering, nothing
Water magnesium sulfate is dried.Filtrate is collected by filtration, and decompression rotation is except solvent, thick product silica gel (200-300 mesh) column chromatography [eluent, V
(petroleum ether): V (ethyl acetate)=10:1], purification obtains weak yellow liquid intermediate 1 (22.2g), productivity 95%.1H NMR
(400MHz,CDCl3) δ: 9.82 (d, J=1.4Hz, 1H), 7.77 (dd, J=8.7,1.5Hz, 2H), 6.93 (dd, J=8.7,
1.5Hz, 2H), 3.97 (dd, J=6.6,1.6Hz, 2H), 1.82 1.65 (m, 2H), 1.50 1.35 (m, 2H), 1.35 1.18
(m, 10H), 0.87 (t, J=6.9Hz, 3H).13C NMR(100MHz,CDCl3)δ:190.45,164.49,132.19,
130.05,114.70,68.25,30.91,29.70,29.31,28.78,25.61,22.42,13.93.
(2) synthesis of intermediate 2
Intermediate 1 (2.34g, 10mmol) and the new pyrroles (30mL, 430mmol) steamed is added in 100mL single port bottle, to
In reaction bulb, logical argon displaced air 10min, is rapidly added catalyst InCl3 (0.11g, 0.5mmol) under argon shield,
Magnetic agitation 5h under room temperature, then in reaction bulb, add NaOH (0.2g, 5mmol) powder continuation stirring 30min, cancellation is reacted.
Decompression distillation, reclaims unnecessary pyrroles, obtains dipyrrylmethanes intermediate, take dipyrrylmethanes intermediate (3.50g, 10mmol) molten
Solution, in 80mL dichloromethane, adds tetrachloroquinone (2.9g, 12mmol), magnetic agitation under room temperature condition, fully oxidized 8h.So
After reaction mixture is placed under argon shield, slowly dropping 37mL boron trifluoride diethyl etherate (300mmol), the slowest after 10min
Add 41.7mL triethylamine (300mmol), after dripping complete follow-up continuous reaction 8h.Reactant liquor is poured into equipped with 200-300 mesh silicon
Coarse filtration in the pillar of glue, with dichloromethane as eluent, organic facies washes 3 times (100mL × 3) with saturated sodium hydroxide solution,
Collecting organic facies, anhydrous sodium sulfate is dried, and filtrate is collected by filtration, and decompression rotation is except solvent, and thick product is through silica gel (200-300 mesh) post
Chromatography [eluent, V (petroleum ether): V (ethyl acetate)=10:1] purification obtains blackish green powder intermediate 2 (2.50g), productivity
63%.1H NMR(400MHz,CDCl3) δ: 7.92 (s, 2H), 7.54 (d, J=8.5Hz, 2H), 7.03 (d, J=8.6Hz, 2H),
6.98 (d, J=3.2Hz, 2H), 6.58 6.53 (m, 2H), 4.06 (t, J=6.4Hz, 2H), 1.86 1.82 (m, 2H), 1.42
1.27 (m, 10H), 0.89 (t, J=7.0Hz, 3H).13C NMR(100MHz,CDCl3)δ:162.11,147.42,142.95,
134.79,132.76,131.51,126.00,118.26,114.84,68.25,30.91,29.70,29.31,28.78,
25.61,22.42,13.93.
(3) synthesis of intermediate 3
Intermediate 2 (1.0g, 2.5mmol), 40mL absolute methanol and 40mL dichloromethane it is sequentially added in 100mL there-necked flask
Alkane, magnetic agitation a few minutes under room temperature, evacuation, it is passed through argon shield, afterwards ICl (0.49g, 3.0mmol) is dissolved in 5mL
In absolute methanol, being added dropwise in reaction bulb with syringe, be further continued for reacting 1h after dropping, whole course of reaction is kept away
Light.Complete through TLC detection raw material fundamental reaction, stopped reaction, in there-necked flask, add 50mL distilled water, extract three with dichloromethane
Secondary (80mL × 3), organic layer washs three times (100mL × 3) through saturated aqueous common salt again, merges organic facies, and anhydrous magnesium sulfate is dried
Overnight.Filtrate is collected by filtration, removes solvent under reduced pressure, thick product silica gel (200-300 mesh) column chromatography [eluent, the V obtained
(petroleum ether): V (dichloromethane)=20:1] purification obtains red solid intermediate 3 (0.78g), productivity 60%.1H NMR
(400MHz,CDCl3) δ: 7.97 (s, 1H), 7.82 (s, 1H), 7.52 (d, J=8.5Hz, 2H), 7.04 (d, J=8.7Hz,
4H), 6.61 (s, 1H), 4.06 (t, J=6.4Hz, 2H), 1.87 1.82 (m, 2H), 1.42 1.31 (m, 10H), 0.89 (t, J
=7.0Hz, 3H).13C NMR(100MHz,CDCl3)δ:162.16,146.83,146.00,145.04,135.93,135.77,
135.04,132.91,132.53,125.68,119.30,114.78,68.47,31.84,29.34,29.25,29.15,
26.05,22.68,14.12.
(4) synthesis of intermediate 4
Be sequentially added in 100mL there-necked flask intermediate 3 (0.26g, 0.5mmol), 4-formylphenylboronic acid (0.12g,
0.75mmol), 20mL oxolane loads onto reflux condensing tube, evacuation, displacement argon shield；Add the four of catalytic amount afterwards
(triphenylphosphine) palladium and K2CO3(2M, 3mL) solution, is warming up to 80 DEG C of backflows overnight；Stopped reaction, is cooled to room temperature, will reaction
Liquid is poured in 100mL distilled water, extracts 3 times (60mL × 3) with dichloromethane, merges organic facies, and organic facies saturated common salt is washed
Three times (100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, and decompression rotation is except solvent, and the crude product obtained is through silicon
Glue (300-400 mesh) column chromatography [eluent, V (petroleum ether): V (dichloromethane)=5:1] purification obtains Red-brown powder intermediate 4
(0.19g), productivity 78%.1H NMR(400MHz,CDCl3)δ:9.99(s,1H),8.29(s,1H),8.00(s,1H),7.89
(d, J=8.0Hz, 2H), 7.69 (d, J=8.0Hz, 2H), 7.59 (d, J=8.5Hz, 2H), 7.22 (s, 1H), 7.10 (s,
1H), 7.07 (d, J=7.2Hz, 2H), 6.62 (d, J=2.5Hz, 1H), 4.08 (t, J=6.4Hz, 2H), 1.88 1.84 (m,
2H), 1.40 1.28 (m, 10H), 0.90 (t, J=6.9Hz, 3H).13C NMR(100MHz,CDCl3)δ:191.49,162.12,
144.95,140.20,139.01,135.49,135.09,132.53,131.98,130.54,125.86,125.65,119.13,
114.80,68.49,31.84,29.35,29.26,29.18,26.07,22.68,14.11.
(5) synthesis of intermediate 5
Intermediate 4 (0.4g, 0.8mmol), 10mL absolute methanol and 10mL DMF is added, in room temperature in 50mL there-necked flask
After lower magnetic agitation a few minutes, evacuation, replace argon shield.Afterwards ICl (0.16g, 1.0mmol) is dissolved in 5mL anhydrous
In methanol, being added dropwise in reaction bulb with syringe, 5min dropping is complete, continues reaction 2h, whole process lucifuge.Through TLC
Detection raw material reaction is complete, stopped reaction, adds 20mL saturated sodium thiosulfate solution in there-necked flask.Continue stirring 15min, instead
Answer liquid dichloromethane to extract 3 times (30mL × 3), 2 times (100mL × 2) of organic facies saturated aqueous common salt washing, after through anhydrous sulfur
Acid magnesium is dried overnight.Filtrate is collected by filtration, and decompression rotation is except solvent, crude on silica gel (300-400 mesh) column chromatography [eluent, V
(petroleum ether): V (dichloromethane)=8:1] purification obtains dark red powder solid intermediate 5 (0.44g), productivity 89%.1H
NMR(400MHz,CDCl3) δ: 10.00 (s, 1H), 8.33 (s, 1H), 8.00 (d, J=7.9Hz, 1H), 7.90 (d, J=
7.4Hz, 2H), 7.69 (d, J=7.8Hz, 2H), 7.58 (d, J=8.2Hz, 2H), 7.27 (s, 1H), 7.15 (s, 1H), 7.09
(d, J=8.3Hz, 2H), 4.09 (t, J=6.3Hz, 2H), 1.90 1.84 (m, 2H), 1.42 1.29 (m, 10H), 0.91 (s,
3H).13C NMR(100MHz,CDCl3)δ:191.42,162.48,147.46,141.89,138.44,136.94,135.34,
132.60,130.55,130.37,128.04,127.15,125.75,125.49,115.01,68.56,31.84,29.34,
29.26,29.15,26.06,22.68,14.12.
(6) synthesis of intermediate 6
Be sequentially added in 100mL there-necked flask paraiodoanisole (1.1g, 4.8mmol), para-bromoaniline (0.34g,
2.0mmol), potassium hydroxide (0.56g, 10mmol), 1,10-phenanthrene quinoline (0.03g, 0.16mmol) and 60mL toluene, load onto back
Stream condensing tube, evacuation, replace argon shield.Flow down at argon, be rapidly added the Cu-lyt. of catalytic amount, be warming up to backflow anti-
Answer 20h.Complete through TLC detection raw material reaction, stopped reaction, remove solvent under reduced pressure, reactant mixture is dissolved in 100mL dichloromethane
Alkane, then wash 3 times (80mL × 3) through saturated aqueous common salt, organic facies is dried overnight through anhydrous sodium sulfate.Filtrate is collected by filtration, subtracts
Pressure rotation is except solvent, and crude on silica gel (200-300 mesh) column chromatography [eluent, V (petroleum ether): V (ethyl acetate)=8:1] is pure
Change and obtain faint yellow solid intermediate 6 (0.60g), productivity 78%.1H NMR(400MHz,CDCl3) δ: 7.31 (d, J=9.0Hz,
2H), 7.04 7.02 (m, 4H), 6.93 6.91 (m, 4H), 6.67 (d, J=9.0Hz, 2H), 3.74 (s, 6H).
(7) synthesis of intermediate 7
Be sequentially added in 100mL there-necked flask intermediate 6 (0.76g, 2.0mmol), duplex pinacol boron ester (0.76g,
3.0mmol), potassium acetate (0.78g, 8.0mmol) and 40mL1,4-dioxane.Evacuation, replaces argon shield, adds catalysis
Pd (dppf) Cl of amount2.Control temperature to react 24h, stopped reaction at 85 DEG C, be cooled to room temperature.Pour reactant liquor into 100mL
In distilled water, 3 times (80mL × 3) of dichloromethane extraction, merge organic facies, organic facies is washed 3 times through saturated aqueous common salt again
(100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, removes solvent, crude on silica gel (200-300 under reduced pressure
Mesh) column chromatography [eluent, V (petroleum ether): V (ethyl acetate)=10:1] purification obtains yellow powder solid intermediate 7
(0.65g), productivity 75%.1H NMR(400MHz,CDCl3) δ: 7.60 (d, J=7.8Hz, 2H), 7.06 (d, J=8.2Hz,
4H), 6.86 (d, J=8.3Hz, 2H), 6.83 (d, J=8.3Hz, 4H), 3.80 (s, 6H), 1.32 (s, 12H).13C NMR
(100MHz,CDCl3)δ:156.12,140.33,135.73,127.12,118.55,114.66,83.39,55.45,24.82.
(8) synthesis of intermediate 8
10-methoxyimino stilbene (0.67g, 3.0mmol) it is sequentially added into, to bromo-iodobenzene in 100mL there-necked flask
(1.3g, 4.5mmol), sodium tert-butoxide (0.58g, 6mmol) and 30mL toluene.Load onto reflux condensing tube, evacuation, replace argon
Protection, is rapidly added the Pd of catalytic amount afterwards2(dba)3With 3-tert-butyl group phosphine, it is warming up to back flow reaction 8h.Stopped reaction, cooling
To room temperature, being poured into by reactant liquor in 100mL distilled water, 3 times (60mL × 3) of dichloromethane extraction, organic facies is again through saturated common salt
3 times (100mL × 3) of water washing, anhydrous sodium sulfate is dried overnight.Filtrate is collected by filtration, and decompression rotation is except solvent, crude on silica gel
(200-300 mesh) column chromatography [eluent, V (petroleum ether): V (ethyl acetate)=20:1] purification obtains in pale yellow oily liquid body
Mesosome 8 (0.62g), productivity 54%.1H NMR(400MHz,CDCl3) δ: 7.81 (dd, J=7.9,1.4Hz, 1H), 7.55 7.50
(m, 1H), 7.45 7.32 (m, 5H), 7.30 (dd, J=7.4,1.5Hz, 1H), 7.10 7.04 (m, 2H), 6.27 6.21 (m,
2H),6.03(s,1H),3.78(s,3H).
(9) synthesis of intermediate 9
Be sequentially added in 100mL there-necked flask intermediate 8 (1.13g, 3.0mmol), duplex pinacol boron ester (1.14g,
4.5mmol), potassium acetate (1.18g, 12.0mmol) and 40mL1,4-dioxane.Obtain by the method for similar synthetic intermediate 7
Light yellow solid intermediate 9 (0.87g), productivity 68%.1H NMR(400MHz,CDCl3) δ: 7.79 (d, J=7.7Hz, 1H),
7.52 7.42 (m, 5H), 7.37 (d, J=7.2Hz, 3H), 7.29 (d, J=7.3Hz, 1H), 6.39 (d, J=8.4Hz, 2H),
6.02(s,1H),3.76(s,3H),1.27(s,12H).13C NMR(100MHz,CDCl3)δ:156.12,150.60,142.63,
135.87,135.70,134.22,130.74,130.01,129.46,129.43,128.32,127.52,127.17,126.98,
110.98,102.15,83.17,55.32,24.77.
(10) synthesis of intermediate 10
2-bromine carbazole (2.45g, 10mmol) it is sequentially added in 100mL there-necked flask, paraiodoanisole (2.58g,
11mmol), Hydro-Giene (Water Science). (190mg, 1mmol), L-PROLINE (230mg, 2mmol), potassium carbonate (2.76g, 20mmol) and
30mL dimethyl sulfoxide.It is warming up to 90 DEG C of reaction 40h.Stopped reaction, is cooled to room temperature, adds 100mL distilled water diluting, mixed liquor
Being extracted with ethyl acetate 3 times (60mL × 3), organic facies washs 3 times (100mL × 3) through saturated aqueous common salt, and anhydrous magnesium sulfate is done
Dry.Filtrate is collected by filtration, and thick product, through silica gel column chromatography, obtains pale solid intermediate 10 (2.3g), productivity 65%.1H
NMR(400MHz,CDCl3) δ: 8.13 (d, J=7.1Hz, 1H), 8.01 (d, J=7.9Hz, 1H), 7.51 7.38 (m, 5H),
7.32 (d, J=7.9Hz, 2H), 7.15 (d, J=7.1Hz, 2H), 3.95 (s, 3H).
(11) synthesis of intermediate 11
In 100mL there-necked flask, be sequentially added into intermediate 10 (3.51g, 10mmol), duplex pinacol boron ester (3.81g,
15mmol).White crystal intermediate 11 (2.7g), productivity 67% is obtained by the method for similar synthetic intermediate 7.1H NMR
(400MHz,CDCl3) δ: 8.19 8.13 (m, 2H), 7.80 7.72 (m, 2H), 7.46 (d, J=8.7Hz, 2H), 7.41 (d, J
=7.4Hz, 1H), 7.30 (d, J=8.6Hz, 2H), 7.13 (d, J=8.6Hz, 2H), 3.94 (s, 3H), 1.36 (s, 12H).
(12) synthesis of intermediate 12
Be sequentially added in 100mL there-necked flask intermediate 5 (0.31g, 0.5mmol), intermediate 7 (0.26g, 0.6mmol),
30mL oxolane and solution of potassium carbonate (2M, 3mL), load onto reflux condensing tube, evacuation, replace argon shield.Again to reaction
Add four (triphenylphosphinyl) palladium of catalytic amount in Ping, be warming up to 80 DEG C of reaction 24h.Stopped reaction, is cooled to room temperature, will reaction
Liquid is poured in 100mL distilled water, 3 times (60mL × 3) of dichloromethane extraction, and organic facies is washed 3 times with saturated aqueous common salt again
(100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, and decompression rotation is except solvent, crude on silica gel (200-300
Mesh) column chromatography [eluent, V (petroleum ether): V (ethyl acetate)=5:1] purification obtains dark green solid intermediate 12
(0.35g), productivity 80%.1H NMR(400MHz,CDCl3)δ:9.98(s,1H),8.30(s,1H),8.24(s,1H),7.88
(d, J=8.1Hz, 2H), 7.68 (d, J=8.1Hz, 2H), 7.61 (d, J=8.5Hz, 2H), 7.34 (d, J=8.6Hz, 2H),
7.17 (s, 1H), 7.11 (s, 1H), 7.08 (s, 6H), 6.92 (d, J=8.6Hz, 2H), 6.84 (d, J=8.8Hz, 4H), 4.09
(t, J=6.4Hz, 2H), 3.80 (s, 6H), 1.89 1.84 (m, 2H), 1.38 1.32 (m, 10H), 0.90 (t, J=5.9Hz,
3H).13C NMR(100MHz,CDCl3)δ:191.56,161.95,156.11,148.62,146.22,143.74,140.49,
139.24,139.15,136.45,135.44,135.23,134.89,132.44,130.53,126.75,126.15,125.97,
125.54,124.96,124.58,123.98,120.39,114.78,110.03,103.82,68.45,55.49,31.83,
29.34,29.25,29.18,26.06,22.67,14.11.MALDI-TOF-MS,m/z:calcd for C50H48BF2N3O4:
803.370,found:803.474[M]+.
(13) synthesis of intermediate 13
Intermediate 5 (0.31g, 0.5mmol), intermediate 9 (0.25g, 0.6mmol) it is sequentially added in 100mL there-necked flask.
Green solid intermediate 13 (0.30g), productivity 74% is obtained by the method for similar synthetic intermediate 12.1H NMR(400MHz,
CDCl3)δ:9.98(s,1H),8.23(s,2H),7.87–7.82(m,3H),7.68(s,2H),7.59–7.54(m,3H),7.47
(d, J=5.7Hz, 2H), 7.42 7.36 (m, 3H), 7.31 (d, J=8.1Hz, 1H), 7.21 (s, 2H), 7.14 (s, 1H),
7.08 (s, 2H), 6.99 (s, 1H), 6.42 (s, 2H), 6.05 (s, 1H), 4.08 (d, J=2.3Hz, 2H), 3.79 (s, 3H),
1.89–1.86(m,2H),1.35–1.29(m,10H),0.90(s,3H).13C NMR(100MHz,CDCl3)δ:191.54,
161.86,156.19,148.33,145.85,144.04,142.82,141.12,138.71,136.52,135.89,135.33,
134.84,134.27,132.42,130.81,130.51,130.12,129.51,128.43,127.62,127.28,127.11,
126.04,125.50,124.65,124.15,121.86,114.74,112.22,106.50,102.27,68.42,55.38,
31.83,29.35,29.25,29.17,26.06,22.68,14.12.MALDI-TOF-MS,m/z:calcd.for
C51H46BF2N3O3:797.360,found:797.169[M]+.
(14) synthesis of intermediate 14
Be sequentially added in 100mL there-necked flask intermediate 5 (0.31g, 0.5mmol), intermediate 11 (0.24g,
0.6mmol).Green solid intermediate 14 (0.30g), productivity 76% is obtained by the method for similar synthetic intermediate 12.1H NMR
(400MHz,CDCl3) δ: 9.99 (s, 1H), 8.38 (s, 1H), 8.28 (s, 1H), 8.12 (dd, J=7.8,2.9Hz, 2H),
7.89 (d, J=8.3Hz, 2H), 7.69 (d, J=8.2Hz, 2H), 7.64 (d, J=8.7Hz, 2H), 7.48 7.43 (m, 4H),
7.42 7.38 (m, 1H), 7.30 (dd, J=8.0,3.6Hz, 2H), 7.23 (s, 1H), 7.20 (s, 1H), 7.17 (d, J=
2.1Hz, 1H), 7.15 (d, J=2.1Hz, 1H), 7.13 (s, 1H), 7.11 (s, 1H), 4.10 (t, J=6.5Hz, 2H), 3.96
(s, 3H), 1.89 1.86 (m, 2H), 1.54 1.36 (m, 10H), 0.91 (t, J=6.9Hz, 3H).13C NMR(100MHz,
CDCl3)δ:191.60,162.08,159.13,146.89,143.78,142.11,141.91,139.74,139.08,
136.27,134.98,132.53,131.70,130.58,130.09,129.85,128.71,126.18,125.89,125.59,
122.88,122.79,120.90,120.28,120.02,117.72,115.37,114.87,109.85,106.33,77.38,
77.06,76.74,68.49,55.67,31.87,29.40,29.30,29.21,26.11,22.73,14.18.MALDI-TOF-
MS,m/z:calcd.for C49H44BF2N3O3:771.340,found:771.214[M]+.
Embodiment 1
The synthesis of Dye 1:
100mL there-necked flask is sequentially added into intermediate 12 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol),
20mL chloroform and 20mL acetonitrile.Load onto reflux condensing tube, evacuation, replace argon shield, be rapidly added 2 piperidines, be warming up to
80 DEG C of back flow reaction 24h.Stopped reaction, is cooled to room temperature, adds 100mL dchloromethane reactant liquor, the saturated food of organic facies
3 times (100mL × 3) of saline washing, anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, and decompression rotation is except solvent, and crude product is through silicon
Glue (300-400 mesh) column chromatography [eluent, V (dichloromethane): V (methanol)=10:1] purification obtains dark green solid powder
Dye1 (0.14g), productivity 80%.1H NMR(400MHz,DMSO-d6) δ: 8.74 (d, J=4.4Hz, 2H), 7.94 7.88 (m,
5H), 7.73 (d, J=8.5Hz, 2H), 7.63 (d, J=8.6Hz, 2H), 7.43 (s, 1H), 7.26 (s, 1H), 7.19 (d, J=
8.5Hz, 2H), 7.03 (d, J=8.8Hz, 4H), 6.92 (d, J=8.9Hz, 4H), 6.74 (d, J=8.7Hz, 2H), 4.11 (t,
J=6.3Hz, 2H), 3.74 (s, 6H), 1.80 1.75 (m, 2H), 1.45 1.28 (m, 10H), 0.86 (t, J=6.2Hz, 3H)
.13C NMR(100MHz,DMSO-d6)δ:163.53,161.92,156.37,154.18,152.63,148.46,146.01,
141.13,140.28,135.37,133.38,130.56,130.12,127.28,126.97,126.95,126.15,125.81,
125.43,120.52,119.65,119.57,117.14,115.47,115.41,109.27,103.34,68.37,55.73,
31.73,29.49,29.15,29.08,26.02,22.56,14.44.MALDI-TOF-MS,m/z:calcd.for
C53H49BF2N4O5:870.380,found:870.196[M]+.
Embodiment 2
The synthesis of Dye 2:
Intermediate 13 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol) it is sequentially added in 100mL there-necked flask.
Green solid powder Dye2 (0.13g), productivity 78% is obtained by the method for similar synthesis Dye1.1H NMR(400MHz,DMSO-
d6) δ: 8.69 (d, J=17.6Hz, 1H), 7.94 7.86 (m, 3H), 7.78 (d, J=8.2Hz, 1H), 7.74 7.69 (m,
1H), 7.65 (dd, J=10.0,4.4Hz, 2H), 7.56 7.38 (m, 7H), 7.35 7.27 (m, 4H), 7.18 (dd, J=
11.7,3.0Hz, 3H), 7.09 7.02 (m, 2H), 6.27 (d, J=4.0Hz, 1H), 6.22 (d, J=9.0Hz, 1H), 4.12
(t, J=8.1Hz, 2H), 3.77 (d, J=7.3Hz, 3H), 1.81 1.76 (m, 2H), 1.46 1.28 (m, 10H), 0.88 (s,
3H).13C NMR(100MHz,DMSO-d6)δ:163.74,161.36,155.86,149.96,147.29,143.78,142.28,
140.98,140.15,137.41,135.99,135.06,134.22,133.33,131.61,130.71,130.11,129.94,
128.27,127.95,127.64,126.02,125.83,124.14,115.36,110.97,102.87,68.39,55.94,
31.72,29.50,29.18,29.05,26.01,22.57,14.43.MALDI-TOF-MS,m/z:calcd.for
C54H47BF2N4O4:864.370,found:864.212[M]+.
Embodiment 3
The synthesis of Dye3:
Intermediate 14 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol) it is sequentially added in 100mL there-necked flask.
Green solid powder Dye3 (0.13g), productivity 75% is obtained by the method for similar synthesis Dye1.1H NMR(400MHz,DMSO-
d6) δ: 8.82 (s, 1H), 8.28 8.22 (m, 2H), 8.02 7.93 (m, 4H), 7.78 (d, J=8.6Hz, 1H), 7.72 7.69
(m, 1H), 7.56 (d, J=8.8Hz, 1H), 7.49 (s, 1H), 7.42 (t, J=7.8Hz, 4H), 7.31 (d, J=7.8Hz,
4H), 7.27 7.21 (m, 4H), 7.06 7.03 (m, 1H), 4.14 (t, J=6.3Hz, 2H), 3.97 3.79 (m, 3H), 1.85
1.71 (m, 2H), 1.52 1.28 (m, 10H), 0.91 (t, J=6.9Hz, 3H).13CNMR(100MHz,DMSO-d6)δ:
163.47,162.03,159.03,146.70,143.85,141.84,141.62,139.42,139.14,135.38,133.47,
132.46,132.06,130.76,130.12,129.93,128.87,126.25,125.86,124.06,122.80,122.51,
121.45,120.92,120.43,118.67,115.83,115.45,110.04,106.82,68.38,55.90,31.74,
29.48,29.17,29.10,26.02,22.58,14.45.MALDI-TOF-MS,m/z:calcd.for C52H45BF2N4O4:
838.350,found:838.991[M]+.
The target dyestuff Dye 1～3 ultra-violet absorption spectrum in dichloromethane solution and electrochemistry in above-described embodiment
The related data of matter is shown in Tables 1 and 2 respectively；In embodiment, the photoelectric properties parameter of target dyestuff Dye 1～3 is shown in Table 3.
The photophysical property of table 1 Dye 1～3
a Maximum absorption in DCM solution(10-5).
bεis the molar extinction coefficient atλmax of the maximum
absorption.
c Maximum absorption on TiO2film.
Be can be seen that by Fig. 1 and table 1 data, three kinds of dyestuffs have covering whole ultraviolet-visible light district (300-850nm),
In addition 3 kinds of dyestuffs all show 3 obvious absworption peaks.The absworption peak that wherein energy is higher is positioned near ultraviolet band 300-
400nm, this is mainly due to the π-π that electronics produces on triphenylamine derivative aromatic ring*Transition, belongs to originally relocating residents from locations to be used for construction of new buildings or factories of donor monomer
Move absworption peak；Dyestuff absworption peak at 450-520nm belongs to the characteristic absorption of BODIPY conjugate unit, mono-owing to BODIPY
π-the π of unit*, S0-S2Migrate；The relatively low one group of absworption peak of energy lays respectively at 627nm, 605nm and 590nm, this mainly due to
π-the π of BODIPY unit*, S0-S1Migrate and donor monomer and jointly being drawn by the intramolecular charge transport (ICT) between body unit
Rise.Compared to dyestuff Dye 2 and Dye 3, dyestuff Dye1 shows the Red Shift Phenomena of 22 and 37nm, this illustrate difference to
The electron donation of body unit is different, and i.e. 4,4-dimethoxy triphenylamine shows strong electron donation, enhances to receptor
Electron transfer between unit, so that λ max moves to long wave direction.
As seen from Figure 2, three kinds of dyestuffs are at solid TiO2Showing good collection optical property on film, maximum absorption band divides
It is not positioned at 632nm, 621nm and 595nm, relative to the absorption spectrum in solution, shows the red of 5nm, 15nm and 5nm respectively
Moving phenomenon, this illustrates that dyestuff there occurs that on titanium dioxide film J-assembles.Additionally, relative to the absorption in solution, three dyes
Material molecule absorption spectrum on film all show a certain degree of widening, indicate dyestuff can active adsorption in TiO2
Film, this is conducive to improving the dyestuff capture rate to sunlight.
The electrochemical properties of table 2 Dye 1～3
[a]E0,0was estimated from the absorption thresholds from absorption
spectra of dyes adsorbed on the TiO2film,E0,0=1240/ λedge abs.
[b]Eox was measured in CH2Cl2and calibrated by addition of 0.63V to the
potential versus Fc/Fc+.
[c]Computed from the formula E* ox=EOX-E0,0.
Can be seen that from table 2 and Fig. 9, the ground state oxidizing potential (E of 3 kinds of dyestuffsoxVs.NHE) all than I3-/I-Electricity to oxygen
Change/reduction potential (0.42V vs.NHE) is corrected, and the oxidation state dye molecule i.e. losing electronics can effectively be reduced by I-；Dye
The excited state reduction potential of material molecule is all more negative than the energy level of the conduction band of titanium dioxide (-0.5V vs.NHE), just can make excited state
Electronics be efficiently injected into the conduction band of quasiconductor, so based on dye cell electronic circulation is fully utilized, thus
These BODIPY dyestuffs can be as the sensitizer of titanium dioxide electrodes.
The photoelectric properties parameter of table 3 Dye 1～3
Can be seen that from table 3 and Figure 10, the J of three kinds of dyestuffsscValue is respectively 8.21,7.35 and 5.77mA cm-2, compared to
The sensitized cells device performance of dyestuff Dye2 and Dye3, Dye1 presents best photovoltaic performance, its short-circuit current density Jsc
For 8.21mA cm-2, open-circuit voltage is 595mV, and fill factor, curve factor is 0.64, and corresponding photoelectric transformation efficiency PCE reaches 3.12%.
The short-circuit current density maximum of Dye1 is mainly due to it and has a more preferable light capture ability, and in corresponding Fig. 1, it has wide
Spectral absorption and high molar extinction coefficient.In dyestuff Dye1～3, the V of Dye3ocBeing worth the highest, this is possibly due to dyestuff Dye3
HOMO energy level minimum, dyestuff regeneration driving force more sufficient, reduce electronics passback speed.
The present invention illustrates detailed synthetic method by above-described embodiment, but the invention is not limited in said method, i.e.
Do not mean that the present invention has to rely on above-mentioned reaction condition and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, the equivalence to reaction dissolvent catalyst of the present invention is replaced and the change etc. of reaction actual conditions, is all fallen
Within the scope of protection scope of the present invention and disclosure.
Claims (6)
1. novel containing BODIPY conjugate unit organic dye sensitized a dose, it is characterised in that this material has logical formula (I)
Chemical constitution:
In formula (I), D is donor monomer, the one in following construction unit:
Wherein, R, R1For H or CnH2n+1Or OCnH2n+1, n is the natural number of 1-20.
The preparation method of a kind of novel containing BODIPY conjugate unit organic dye sensitized dose the most as claimed in claim 1, its
It is characterised by, comprises the following steps:
(1) under the effect of alkali, hydroxy benzaldehyde, through alkylated reaction, prepares intermediate 1, and its structure is:
(2) intermediate 1 and pyrroles are condensed to yield two pyrrolidine intermediate, two pyrrolidines under triethylamine effect with boron trifluoride second
Ether complex reaction obtains intermediate 2, and its structure is:
(3) intermediate 2 and iodine monochloride are through electrophilic substitution reaction, prepare intermediate 3, and its structure is:
(4) intermediate 3 under the effect of four (triphenylphosphinyl) palladium with 4-formylphenylboronic acid through Suzuki coupling reaction, prepare
Intermediate 4, its structure is:
(5) intermediate 4 again with iodine monochloride through electrophilic substitution reaction, prepare intermediate 5, its structure is:
(6) to alkoxyl iodobenzene and para-bromoaniline through ullmann reaction, obtaining intermediate 6, its structure is:
(7) intermediate 6 is through Suzuki coupling reaction under the catalytic action of four (triphenylphosphinyl) palladium, prepares intermediate 7, its knot
Structure is:
(8) 10-Alkoximino stilbene with to bromo-iodobenzene through Buchwald Hartwig coupling reaction, obtain intermediate 8, its knot
Structure is:
(9) intermediate 8 is through Suzuki coupling reaction under the catalytic action of four (triphenylphosphinyl) palladium, obtains intermediate 9, its knot
Structure is:
(10) will to alkoxyl iodobenzene and 2-bromine carbazole under Hydro-Giene (Water Science). is catalyzed through Liv Ullmann condensation reaction, prepare intermediate
10, its structure is:
(11) by intermediate 10 with duplex pinacol boron ester through Suziki coupling reaction, prepare intermediate 11, its structure is:
(12) intermediate 7, intermediate 9 and intermediate 11 respectively with intermediate 5 through Suzuki coupling reaction, prepare intermediate 12,
13,14, its structure is:
D is
(13) intermediate 12,13,14 respectively under the effect of cyanoacetic acid through Knoevenagel condensation reaction, prepare target respectively
Dyestuff Dye1,2,3, its structure is:
A kind of novel preparation method containing organic dye sensitized dose of BODIPY class conjugate unit the most as claimed in claim 2, its
Being characterised by, in step (1)-(13), the reaction medium of described reaction is acetonitrile, DMF, methanol, tetrahydrochysene furan
Mutter, one or more mixing in dichloromethane, 1,4-dioxane, toluene, chloroform, ethanol.
A kind of novel preparation method containing organic dye sensitized dose of BODIPY class conjugate unit the most as claimed in claim 2, its
Be characterised by, described in step (2), (6), (8), (11), (12) and (13) reaction in, catalyst used be Indium-111 chloride,
One in four (triphenylphosphinyl) palladium, three (dibenzalacetone) two palladium, Cu-lyt., Hydro-Giene (Water Science). and piperidines.
A kind of novel preparation method containing organic dye sensitized dose of BODIPY class conjugate unit the most as claimed in claim 2, its
It is characterised by, in step (1), (4), (6), (7), (8), (9), (10), (11), (12) and (13) described reaction, alkali used
For the one in potassium carbonate, triethylamine, potassium hydroxide, potassium acetate, piperidines and sodium tert-butoxide.
A kind of novel preparation method containing organic dye sensitized dose of BODIPY class conjugate unit the most as claimed in claim 2, its
Being characterised by, in step (1)-(13), the reaction temperature in described reaction is 25-120 DEG C, and the response time is 2-48h.
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| JP2019172826A (en) * | 2018-03-28 | 2019-10-10 | 富士フイルム株式会社 | Fluorescent compound and florescent label biological material using the same |
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