CN106221280B - Organic dye sensitizer containing BODIPY conjugated units and preparation method thereof - Google Patents
Organic dye sensitizer containing BODIPY conjugated units and preparation method thereof Download PDFInfo
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- CN106221280B CN106221280B CN201610648381.3A CN201610648381A CN106221280B CN 106221280 B CN106221280 B CN 106221280B CN 201610648381 A CN201610648381 A CN 201610648381A CN 106221280 B CN106221280 B CN 106221280B
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- organic dye
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- dye
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- 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 6
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 3
- 239000000543 intermediate Substances 0.000 claims description 98
- 239000000975 dye Substances 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 46
- 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 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkoxy iodobenzene Chemical compound 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 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
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- 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
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- 150000003235 pyrrolidines Chemical class 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical class 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
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 3
- 235000021286 stilbenes Nutrition 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
- 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
- 230000000694 effects Effects 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 2
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000005406 washing 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 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
- 0 *C1C=CC(N(c(cc2)ccc2Br)c(cc2)ccc2I)=CC1 Chemical compound *C1C=CC(N(c(cc2)ccc2Br)c(cc2)ccc2I)=CC1 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 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
- 230000008859 change Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002027 dichloromethane extract Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 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
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- IWCBFNUUALXQBB-UHFFFAOYSA-N B(O)(O)O.B(F)(F)F Chemical group 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
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur 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
- 230000021615 conjugation Effects 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
- 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
- 239000002159 nanocrystal Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 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
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 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
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
Abstract
The invention discloses a BODIPY organic dye sensitizer 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 the advantages of simple molecular synthesis method, easy control, high yield and 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 the quick magnificent solar cell material field of dyestuff, a kind of conjugate unit of class containing BODIPY is specifically related to
Organic dye sensitized dose.
Background technology：
Switzerland since 1991Group is used as dyestuff and nanoporous TiO using bipyridyl ruthenium first2Film preparation
Since DSSC (DSSCs), dye sensitized nano crystal TiO2Solar cell just relies on low preparation cost
Higher photoelectric transformation efficiency turns into the study hotspot in solar energy photoelectric conversion field in the late two decades.BODIPY parent nucleus has
Multiple avtive spots, can be according to calorifics, optically and electrically performance requirement carries out appropriate modification and functionalization.It is right that people pass through
Each site of BODIPY parent nucleus is modified, and has synthesized the novel B ODIPY dyestuffs of many excellent performances.Researchers generally select
Select and modified on two pyrrole rings of BODIPY parents, can effective extension body by introducing the functional group of different performance
System's conjugation chain length, increases the rigid planar structure of core, wherein introducing substituent on 3, the 5- positions of parent nucleus and 2,6-
Maximum is influenceed on the spectrum property of dye molecule.2,6- are modified the BODIPY dye sensitizing agents to acceptor electron group 2012
Year is the report such as Dai, and they have been synthesized using BODIPY as conjugated pi bridge, and benzimidizole derivatives are donor monomer, and cyanoacetic acid is suction
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 the highest photoelectric transformation efficiency at that time based on BODIPY dye-sensitized cell devices, presents huge application potential.So
And, the efficiency on the BODIPY dye sensitizing agents of this kind of 2,6- modifications is not significantly improved always.
Triphenylamine is the excellent electron transport material of another kind of photoelectric properties, because it has strong electron donation and original
Material is cheap to be easy to get, and is increasingly widely used in DSSC fields.But its nonplanar stereochemical structure is reduced to light
Absorption, therefore we combine BODIPY units with the triphenylamine derivative of different rigidity, it is desirable to improve dyestuff to light
Absorption and light capture rate, so as to improve the performance of battery.By changing the rigid planar structure of donor, different donors are studied
The electron donation size of unit is to the spectrum of dyestuff and the regulating and controlling effect of energy level, so as to improve battery performance parameter.
The content of the invention：
It is an object of the invention to provide a kind of organic dye sensitized dose of conjugate unit of class containing BODIPY, with novel molecule
Structure, have relatively low edge energy, wide spectral absorption scope, and its preparation method is simple, and synthetic ratio is high.
It is a further object to provide the preparation method of organic dye sensitized dose of the conjugate unit of class containing BODIPY,
Its preparation method is simple, and purifying products are simple, and yield is high, and with universality.
To achieve the above object, the present invention uses following technical scheme：
A kind of organic dye sensitized dose of conjugate unit containing BODIPY, the material has the chemical constitution of logical formula (I)：
In formula (I), D is donor monomer, is one kind in following construction unit：
Wherein, R, R1For H or CnH2n+1Alkyl or alkoxy, n are 1-20 natural number.
A kind of organic dye sensitized dose of preparation method of conjugate unit containing BODIPY, comprises the following steps：
(1) in the presence of alkali, intermediate 1 is made through alkylated reaction in parahydroxyben-zaldehyde, and its structure is：
(2) intermediate 1 and pyrroles are condensed to yield two pyrrolidines intermediates, two pyrrolidines under triethylamine effect with it is borontrifluoride
Borate ether complex reaction obtains intermediate 2, and its structure is：
(3) intermediate 3 is made with iodine monochloride through electrophilic substitution reaction in intermediate 2, and its structure is：
(4) intermediate 3 in the presence of four (triphenylphosphinyl) palladiums with 4- formylphenylboronic acids through Suzuki coupling reactions,
Intermediate 4 is made, its structure is：
(5) intermediate 5 is made again with iodine monochloride through electrophilic substitution reaction in intermediate 4, and its structure is：
(6) ullmann reaction is passed through to alkoxy iodobenzene and para-bromoaniline, obtains intermediate 6, its structure is：
(7) intermediate 7 is made through Suzuki coupling reactions under the catalytic action of four (triphenylphosphinyl) palladiums in intermediate 6,
Its structure is：
(8) 10- Alkoximinos stilbene with to bromo-iodobenzene through Buchwald-Hartwig coupling reactions, obtain intermediate 8,
Its structure is：
(9) intermediate 8 obtains intermediate 9 through Suzuki coupling reactions under the catalytic action of four (triphenylphosphinyl) palladiums,
Its structure is：
(10) Liv Ullmann condensation reaction will be passed through under cuprous iodide catalysis to alkoxy iodobenzene and 2- bromines carbazole, in being made
Mesosome 10, its structure is：
(11) intermediate 10 and duplex pinacol boron ester are passed through into Suziki coupling reactions, intermediate 11, its structure is made
For：
(12) intermediate is made respectively with intermediate 5 through Suzuki coupling reactions in intermediate 7, intermediate 9 and intermediate 11
12nd, 13,14, its structure is：
D is
(13) intermediate 12,13,14 is made respectively respectively in the presence of cyanoacetic acid through Knoevenagel condensation reactions
Target dyestuff Dye1,2,3, its structure is：
As the preferred of above-mentioned technical proposal, in step (1)-(13), the reaction medium of the reaction is acetonitrile, N, N- bis-
One or more in NMF, methanol, tetrahydrofuran, dichloromethane, 1,4- dioxane, toluene, chloroform, ethanol are mixed
Close.
As the preferred of above-mentioned technical proposal, in being reacted described in step (2), (6), (8), (11), (12) and (13), institute
Catalyst is indium trichloride, four (triphenylphosphinyl) palladiums, three (dibenzalacetone) two palladium, stannous chloride, cuprous iodide
With one kind in piperidines.
As the preferred of above-mentioned technical proposal, step (1), (4), (6), (7), (8), (9), (10), (11), (12) and
(13) in the reaction, alkali used is one in potassium carbonate, triethylamine, potassium hydroxide, potassium acetate, piperidines and sodium tert-butoxide
Kind.
As the preferred of above-mentioned technical proposal, in step (1)-(13), the reaction temperature in the reaction is 25-120 DEG C,
Reaction time is 2-48h.
The invention has the advantages that：
(1) in synthetic method, this 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, applied to DSSC, with high compared to the dyestuff of document report
Photoelectric transformation efficiency.
Brief description of the drawings：
Fig. 1 is ultra-violet absorption spectrums of the Dye 1-3 in dichloromethane solution；
Fig. 2 is Dye1-3 in TiO2Normalized uv-visible absorption spectra on film；
Fig. 3 is Dye 1 nucleus magnetic hydrogen spectrum；
Fig. 4 composes for Dye 1 nuclear-magnetism carbon；
Fig. 5 is Dye 2 nucleus magnetic hydrogen spectrum；
Fig. 6 composes for Dye 2 nuclear-magnetism carbon；
Fig. 7 is Dye 3 nucleus magnetic hydrogen spectrum；
Fig. 8 composes for Dye 3 nuclear-magnetism carbon；
Fig. 9 is cyclic voltammetry curves of the Dye 1-3 in dichloromethane solution；
Figure 10 is the I-V curve that Dye 1-3 prepare organic dye sensitized solar cell.
Embodiment：
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 solution
The present invention is released, any restriction will not be constituted to the present invention.
(1) synthesis of intermediate 1
Sequentially added in 500mL round-bottomed flask parahydroxyben-zaldehyde (12.5g, 0.1mol), potassium carbonate (16.5g,
0.12mol), n-octane bromide (23.2g, 0.12mol) and 150mL acetonitriles, magnetic agitation control reaction temperature anti-in 80oC
Answer 10h.Stop reaction, be removed by filtration solid residue with suction funnel, be spin-dried for solvent, with dchloromethane, massive laundering, nothing
Water magnesium sulfate is dried.Filtrate is collected by filtration, decompression rotation removes solvent, crude product silica gel (200-300 mesh) column chromatography [eluent, V
(petroleum ether):V (ethyl acetate)=10:1], purifying obtains weak yellow liquid intermediate 1 (22.2g), yield 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 pyrroles (30mL, 430mmol) newly steamed are added in 100mL single port bottles, to
Lead to argon gas displaced air 10min in reaction bulb, catalyst InCl3 (0.11g, 0.5mmol) is rapidly added under argon gas protection,
Magnetic agitation 5h, then add NaOH (0.2g, 5mmol) powder continuation stirring 30min into reaction bulb at room temperature, is quenched reaction.
Vacuum distillation, reclaims unnecessary pyrroles, obtains dipyrrylmethanes intermediate, take dipyrrylmethanes intermediate (3.50g, 10mmol) molten
Solution adds magnetic agitation, fully oxidized 8h under tetrachloroquinone (2.9g, 12mmol), room temperature condition in 80mL dichloromethane.So
Reaction mixture is placed under argon gas protection afterwards, is slowly added dropwise slow again after 37mL BFEEs (300mmol), 10min
Add after 41.7mL triethylamines (300mmol), completion of dropping and continue to react after 8h.Reaction solution is poured into equipped with 200-300 mesh silicon
Coarse filtration in the pillar of glue, using dichloromethane as eluent, organic phase washes 3 times (100mL × 3) with saturation sodium hydroxide solution,
Organic phase is collected, filtrate is collected by filtration in anhydrous sodium sulfate drying, and decompression rotation removes solvent, and crude product is through silica gel (200-300 mesh) post
Chromatograph [eluent, V (petroleum ether):V (ethyl acetate)=10:1] blackish green powdered intermediate 2 (2.50g), yield are purified to obtain
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 methanols and 40mL dichloromethanes are sequentially added into 100mL there-necked flasks
Alkane, at room temperature magnetic agitation a few minutes, is vacuumized, and is passed through argon gas protection, ICl (0.49g, 3.0mmol) is dissolved in into 5mL afterwards
In absolute methanol, it is added dropwise to syringe in reaction bulb, is further continued for reacting 1h after completion of dropping, whole course of reaction is kept away
Light.It is complete through TLC detections raw material fundamental reaction, stop reaction, 50mL distilled water is added into there-necked flask, three are extracted with dichloromethane
Secondary (80mL × 3), organic layer merges organic phase again through saturated common salt water washing three times (100mL × 3), and anhydrous magnesium sulfate is dried
Overnight.Filtrate is collected by filtration, solvent is removed under reduced pressure, obtained crude product silica gel (200-300 mesh) column chromatography [eluent, V
(petroleum ether):V (dichloromethane)=20:1] red solid intermediate 3 (0.78g), yield 60% are purified to obtain.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
Sequentially added into 100mL there-necked flasks intermediate 3 (0.26g, 0.5mmol), 4- formylphenylboronic acids (0.12g,
0.75mmol), 20mL tetrahydrofurans load onto reflux condensing tube, vacuumize, displacement argon gas protection；The four of catalytic amount is added afterwards
(triphenylphosphine) palladium and K2CO3(2M, 3mL) solution, is warming up to 80 DEG C of backflows and stays overnight；Stop reaction, be cooled to room temperature, will react
Liquid is poured into 100mL distilled water, and 3 times (60mL × 3) are extracted with dichloromethane, merges organic phase, the washing of organic phase saturated common salt
Three times (100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, decompression rotation removes solvent, and obtained crude product is through silicon
Glue (300-400 mesh) column chromatography [eluent, V (petroleum ether):V (dichloromethane)=5:1] Red-brown powder intermediate 4 is purified to obtain
(0.19g), yield 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 methanols and 10mL DMF are added in 50mL there-necked flasks, in room temperature
After lower magnetic agitation a few minutes, vacuumize, displacement argon gas protection.ICl (0.16g, 1.0mmol) is dissolved in 5mL afterwards anhydrous
In methanol, it is added dropwise to syringe in reaction bulb, 5min completion of dropping, continues to react 2h, whole process lucifuge.Through TLC
Detection raw material has been reacted, and stops reaction, and 20mL saturated sodium thiosulfate solution is added into there-necked flask.Continue to stir 15min, instead
Liquid dichloromethane is answered to extract 3 times (30mL × 3), organic phase saturated common salt water washing 2 times (100mL × 2), most afterwards through anhydrous sulphur
Sour magnesium is dried overnight.Filtrate is collected by filtration, decompression rotation removes solvent, crude on silica gel (300-400 mesh) column chromatography [eluent, V
(petroleum ether):V (dichloromethane)=8:1] purifying obtains dark red powder solid intermediate 5 (0.44g), yield 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
Sequentially added into 100mL there-necked flasks paraiodoanisole (1.1g, 4.8mmol), para-bromoaniline (0.34g,
2.0mmol), potassium hydroxide (0.56g, 10mmol), 1,10- ferrosins (0.03g, 0.16mmol) and 60mL toluene, are loaded onto back
Condenser pipe is flowed, is vacuumized, displacement argon gas protection.Under argon gas stream, the stannous chloride of catalytic amount is rapidly added, backflow is warming up to anti-
Answer 20h.Reacted through TLC detection raw materials, stopped reaction, remove solvent under reduced pressure, reactant mixture is dissolved in 100mL dichloromethanes
Alkane, then through saturated common salt water washing 3 times (80mL × 3), organic phase is stayed overnight through anhydrous sodium sulfate drying.Filtrate is collected by filtration, subtracts
Pressure rotation removes solvent, crude on silica gel (200-300 mesh) column chromatography [eluent, V (petroleum ether):V (ethyl acetate)=8:1] it is pure
Change obtains faint yellow solid intermediate 6 (0.60g), yield 78%.1H NMR(400MHz,CDCl3)δ:7.31 (d, J=9.0Hz,
2H), (s, the 6H) of 7.04-7.02 (m, 4H), 6.93-6.91 (m, 4H), 6.67 (d, J=9.0Hz, 2H), 3.74
(7) synthesis of intermediate 7
Sequentially added into 100mL there-necked flasks intermediate 6 (0.76g, 2.0mmol), duplex pinacol boron ester (0.76g,
3.0mmol), potassium acetate (0.78g, 8.0mmol) and 40mL1,4- dioxane.Vacuumize, displacement argon gas protection adds catalysis
Pd (dppf) Cl of amount2.Temperature control is reacted into 24h at 85 DEG C, stops reaction, is cooled to room temperature.Reaction solution is poured into 100mL
In distilled water, dichloromethane extracts 3 times (80mL × 3), merges organic phase, organic phase is again through saturated common salt water washing 3 times
(100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, solvent, crude on silica gel (200-300 is removed under reduced pressure
Mesh) column chromatography [eluent, V (petroleum ether):V (ethyl acetate)=10:1] purifying obtains yellow powder solid intermediate 7
(0.65g), yield 75%.1H NMR(400MHz,CDCl3)δ:7.60 (d, J=7.8Hz, 2H), 7.06 (d, J=8.2Hz,
4H), (s, the 12H) of 6.86 (d, J=8.3Hz, 2H), 6.83 (d, J=8.3Hz, 4H), 3.80 (s, 6H), 1.3213C 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- methoxyiminos stilbene (0.67g, 3.0mmol) is sequentially added in 100mL there-necked flasks, to bromo-iodobenzene
(1.3g, 4.5mmol), sodium tert-butoxide (0.58g, 6mmol) and 30mL toluene.Reflux condensing tube is loaded onto, is vacuumized, argon gas is replaced
Protection, is rapidly added the Pd of catalytic amount afterwards2(dba)3With 3- tert-butyl group phosphines, back flow reaction 8h is warming up to.Stop reaction, cooling
To room temperature, reaction solution is poured into 100mL distilled water, dichloromethane extracts 3 times (60mL × 3), and organic phase is again through saturated common salt
Water washing 3 times (100mL × 3), anhydrous sodium sulfate drying is stayed overnight.Filtrate is collected by filtration, decompression rotation removes solvent, crude on silica gel
(200-300 mesh) column chromatography [eluent, V (petroleum ether):V (ethyl acetate)=20:1] purifying is obtained in pale yellow oily liquid
Mesosome 8 (0.62g), yield 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
Sequentially added into 100mL there-necked flasks intermediate 8 (1.13g, 3.0mmol), duplex pinacol boron ester (1.14g,
4.5mmol), potassium acetate (1.18g, 12.0mmol) and 40mL1,4- dioxane.Obtained with the method for similar synthetic intermediate 7
Light yellow solid intermediate 9 (0.87g), yield 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
Sequentially add 2- bromines carbazole (2.45g, 10mmol) into 100mL there-necked flasks, paraiodoanisole (2.58g,
11mmol), cuprous iodide (190mg, 1mmol), L-PROLINE (230mg, 2mmol), potassium carbonate (2.76g, 20mmol) and
30mL dimethyl sulfoxide (DMSO)s.It is warming up to 90 DEG C of reaction 40h.Stop reaction, be cooled to room temperature, plus 100mL distilled water dilutings, mixed liquor
It is extracted with ethyl acetate 3 times (60mL × 3), organic phase is done through saturated common salt water washing 3 times (100mL × 3), anhydrous magnesium sulfate
It is dry.Filtrate is collected by filtration, crude product obtains pale solid intermediate 10 (2.3g), yield 65% through silica gel column chromatography.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),
(s, the 3H) of 7.32 (d, J=7.9Hz, 2H), 7.15 (d, J=7.1Hz, 2H), 3.95
(11) synthesis of intermediate 11
Into 100mL there-necked flasks, sequentially add intermediate 10 (3.51g, 10mmol), duplex pinacol boron ester (3.81g,
15mmol).White crystal intermediate 11 (2.7g), yield 67% are obtained with 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
Sequentially added into 100mL there-necked flasks intermediate 5 (0.31g, 0.5mmol), intermediate 7 (0.26g, 0.6mmol),
30mL tetrahydrofurans and solution of potassium carbonate (2M, 3mL), load onto reflux condensing tube, vacuumize, displacement argon gas protection.Again to reaction
Four (triphenylphosphinyl) palladiums of catalytic amount are added in bottle, 80oC reactions 24h is warming up to.Stop reaction, be cooled to room temperature, will react
Liquid is poured into 100mL distilled water, and dichloromethane extracts 3 times (60mL × 3), and organic phase uses saturated common salt water washing 3 times again
(100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, decompression rotation removes solvent, crude on silica gel (200-300
Mesh) column chromatography [eluent, V (petroleum ether):V (ethyl acetate)=5:1] purifying obtains dark green solid intermediate 12
(0.35g), yield 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) are sequentially added into 100mL there-necked flasks.
Green solid intermediate 13 (0.30g), yield 74% are obtained with 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
Sequentially added into 100mL there-necked flasks intermediate 5 (0.31g, 0.5mmol), intermediate 11 (0.24g,
0.6mmol).Green solid intermediate 14 (0.30g), yield 76% are obtained with 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
Dye 1 synthesis：
Sequentially added in 100mL there-necked flasks intermediate 12 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol),
20mL chloroforms and 20mL acetonitriles.Reflux condensing tube is loaded onto, is vacuumized, displacement argon gas protection is rapidly added 2 drop piperidines, is warming up to
80 DEG C of back flow reaction 24h.Stop reaction, be cooled to room temperature, add 100mL dchloromethane reaction solutions, organic phase saturation food
Salt water washing 3 times (100mL × 3), anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration, decompression rotation removes solvent, and crude product is through silicon
Glue (300-400 mesh) column chromatography [eluent, V (dichloromethane):V (methanol)=10:1] purifying obtains dark green solid powder
Dye1 (0.14g), yield 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
Dye 2 synthesis：
Intermediate 13 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol) are sequentially added in 100mL there-necked flasks.
Green solid powder Dye2 (0.13g), yield 78% are obtained with similar synthesis Dye1 method.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
Dye3 synthesis：
Intermediate 14 (0.16g, 0.2mmol), cyanoacetic acid (0.04g, 0.4mmol) are sequentially added in 100mL there-necked flasks.
Green solid powder Dye3 (0.13g), yield 75% are obtained with similar synthesis Dye1 method.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-
(t, J=6.9Hz, the 3H) of 1.71 (m, 2H), 1.52-1.28 (m, 10H), 0.9113C NMR(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]+.
Ultra-violet absorption spectrums and electrochemistry of the target dyestuff Dye 1~3 in dichloromethane solution in above-described embodiment
The related data of matter is shown in Tables 1 and 2 respectively；Target dyestuff Dye 1~3 photoelectric properties parameter is shown in Table 3 in embodiment.
The Dye 1~3 of table 1 photophysical property
a Maximum absorption in DCM solution(10-5).
b εis the molar extinction coefficient atλmax of the maximum
absorption.
c Maximum absorption on TiO2film.
It can be seen that by Fig. 1 and the data of table 1, three kinds of dyestuffs have covering in whole ultraviolet-visible light area (300-850nm),
In addition 3 kinds of dyestuffs all show 3 obvious absworption peaks.Wherein the higher absworption peak of energy is located near ultraviolet band 300-
400nm, this is mainly due to the π-π that electronics is produced on triphenylamine derivative aromatic ring*Transition, belongs to originally relocating residents from locations to be used for construction of new buildings or factories for donor monomer
Move absworption peak；Absworption peak of the dyestuff at 450-520nm belongs to the characteristic absorption of BODIPY conjugate units, is attributed to BODIPY mono-
π-the π of member*, S0-S2Migration；One group of relatively low absworption peak of energy respectively be located at 627nm, 605nm and 590nm, this mainly due to
π-the π of BODIPY units*, S0-S1Migration and the intramolecular charge transport (ICT) between donor monomer and receptor unit are drawn jointly
Rise.Compared to dyestuff Dye 2 and Dye 3, dyestuff Dye1 shows 22 and 37nm Red Shift Phenomena, this illustrate difference to
The electron donation of body unit is different, i.e. 4,4- dimethoxy triphenylamines show strong electron donation, enhanced to acceptor
Electro transfer between unit, so that λ max are moved to long wave direction.
As seen from Figure 2, three kinds of dyestuffs are in solid TiO2Good collection optical property, maximum absorption band point are shown on film
Not Wei Yu 632nm, 621nm and 595nm, relative to the absorption spectrum in solution, the red of 5nm, 15nm and 5nm is shown respectively
Phenomenon is moved, this illustrates that dyestuff there occurs that J- assembles on titanium dioxide film.In addition, relative to the absorption in solution, three dyes
Expect absorption spectrum of the molecule on film show it is a certain degree of widen, TiO can be effectively adsorbed in by indicating dyestuff2
Film, this is conducive to improving capture rate of the dyestuff to sunshine.
The Dye 1~3 of table 2 electrochemical properties
[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.
It can be seen that from table 2 and Fig. 9, the ground state oxidizing potential (E of 3 kinds of dyestuffsoxVs.NHE I) is compared3-/I-Electricity to oxygen
Change/reduction potential (0.42V vs.NHE) is corrected, that is, lose the oxidation state dye molecule of electronics effectively can be reduced by I-；Dye
Expect that energy level (- 0.5V vs.NHE) of the excitation state reduction potential of molecule than the conduction band of titanium dioxide is more negative, can just make excitation state
Electronics be efficiently injected into the conduction band of semiconductor, so electronic circulation based on dye cell is fully utilized, thus
These BODIPY dyestuffs can as titanium dioxide electrodes sensitizer.
The Dye 1~3 of table 3 photoelectric properties parameter
It can be seen that from table 3 and Figure 10, the J of three kinds of dyestuffsscValue is respectively 8.21,7.35 and 5.77mAcm-2, compared to
Dyestuff Dye2 and Dye3, Dye1 sensitized cells device performance present best photovoltaic performance, its short-circuit current density Jsc
For 8.21mAcm-2, open-circuit voltage is 595mV, and fill factor, curve factor is 0.64, and corresponding photoelectric transformation efficiency PCE reaches 3.12%.
Dye1 short-circuit current density maximum, which is mainly due to it, has more preferable light capture ability, corresponded to its in Fig. 1 have it is wide
Spectral absorption and high molar extinction coefficient.In dyestuff Dye1~3, Dye3 VocIt is worth highest, this is probably because dyestuff Dye3
HOMO energy levels it is minimum, dyestuff regeneration driving force it is more sufficient, reduce electronics passback speed.
The present invention illustrates detailed synthetic method by above-described embodiment, but the invention is not limited in the above method, i.e.,
Do not mean that the present invention has to rely on above-mentioned reaction condition and could implemented.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, change of equivalence replacement and reaction actual conditions to reaction dissolvent catalyst of the present invention etc., fall
Within the scope of protection scope of the present invention and disclosure.
Claims (6)
1. organic dye sensitized dose of a kind of conjugate unit containing BODIPY, it is characterised in that the material has the chemistry of logical formula (I)
Structure：
In formula (I), D is donor monomer, is one kind in following construction unit：
Wherein, R, R1For H or CnH2n+1Or OCnH2n+1, n is 1-20 natural number.
2. a kind of organic dye sensitized dose of preparation method of conjugate unit containing BODIPY as claimed in claim 1, its feature
It is, comprises the following steps：
(1) in the presence of alkali, intermediate 1 is made through alkylated reaction in parahydroxyben-zaldehyde, and its structure is：
(2) intermediate 1 and pyrroles are condensed to yield two pyrrolidines intermediates, two pyrrolidines under triethylamine effect with boron trifluoride second
Ether complex reaction obtains intermediate 2, and its structure is：
(3) intermediate 3 is made with iodine monochloride through electrophilic substitution reaction in intermediate 2, and its structure is：
(4) intermediate 3 in the presence of four (triphenylphosphinyl) palladiums with 4- formylphenylboronic acids through Suzuki coupling reactions, be made
Intermediate 4, its structure is：
(5) intermediate 5 is made again with iodine monochloride through electrophilic substitution reaction in intermediate 4, and its structure is：
(6) ullmann reaction is passed through to alkoxy iodobenzene and para-bromoaniline, obtains intermediate 6, its structure is：
(7) intermediate 7 is made through Suzuki coupling reactions under the catalytic action of four (triphenylphosphinyl) palladiums in intermediate 6, and it is tied
Structure is：
(8) 10- Alkoximinos stilbene to bromo-iodobenzene with, through Buchwald-Hartwig coupling reactions, obtaining intermediate 8, and it is tied
Structure is：
(9) intermediate 8 obtains intermediate 9 through Suzuki coupling reactions under the catalytic action of four (triphenylphosphinyl) palladiums, and it is tied
Structure is：
(10) Liv Ullmann condensation reaction will be passed through under cuprous iodide catalysis to alkoxy iodobenzene and 2- bromines carbazole, intermediate is made
10, its structure is：
(11) intermediate 10 and duplex pinacol boron ester are passed through into Suziki coupling reactions, intermediate 11 is made, its structure is：
(12) intermediate 7, intermediate 9 and intermediate 11 be respectively with intermediate 5 through Suzuki coupling reactions, be made intermediate 12,
13rd, 14, its structure is：
D is
(13) target is made respectively in the presence of cyanoacetic acid through Knoevenagel condensation reactions in intermediate 12,13,14 respectively
Dyestuff Dye1,2,3, its structure is：
3. a kind of preparation method of organic dye sensitized dose of the conjugate unit of class containing BODIPY as claimed in claim 2, its feature
Be, in step (1)-(13), the reaction medium of the reaction is acetonitrile, DMF, methanol, tetrahydrofuran,
One or more of mixing in dichloromethane, 1,4- dioxane, toluene, chloroform, ethanol.
4. a kind of preparation method of organic dye sensitized dose of the conjugate unit of class containing BODIPY as claimed in claim 2, its feature
It is, in being reacted described in step (2), (6), (8), (11), (12) and (13), catalyst used is indium trichloride, four (three
Phenyl phosphino-) one kind in palladium, three (dibenzalacetone) two palladium, stannous chloride, cuprous iodide and piperidines.
5. a kind of preparation method of organic dye sensitized dose of the conjugate unit of class containing BODIPY as claimed in claim 2, its feature
It is, in step (1), (4), (6), (7), (8), (9), (10), (11), (12) and (13) described reaction, alkali used is carbon
One kind in sour potassium, triethylamine, potassium hydroxide, potassium acetate, piperidines and sodium tert-butoxide.
6. a kind of preparation method of organic dye sensitized dose of the conjugate unit of class containing BODIPY as claimed in claim 2, its feature
It is, in step (1)-(13), the reaction temperature in the reaction is 25-120 DEG C, and the reaction time is 2-48h.
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| CN1715919A (en) * | 2005-07-12 | 2006-01-04 | 大连理工大学 | Fluoroboric dye fluorescent probe for cell zinc ion detection |
| CN103242355A (en) * | 2013-05-10 | 2013-08-14 | 南京大学 | BODIPY (Boron Dipyrromethene) compound-based lysosome fluorescence probe as well as preparation method and applications thereof |
| CN105238092A (en) * | 2015-10-30 | 2016-01-13 | 东莞理工学院 | Novel 2,6-site-substituted BODIPY organic dye sensitizer and preparation method therefor |
| CN105669734A (en) * | 2016-03-16 | 2016-06-15 | 东南大学 | BCPA-BODIPY fluorescent molecules and preparation method and application thereof |
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| CN1715919A (en) * | 2005-07-12 | 2006-01-04 | 大连理工大学 | Fluoroboric dye fluorescent probe for cell zinc ion detection |
| CN103242355A (en) * | 2013-05-10 | 2013-08-14 | 南京大学 | BODIPY (Boron Dipyrromethene) compound-based lysosome fluorescence probe as well as preparation method and applications thereof |
| CN105238092A (en) * | 2015-10-30 | 2016-01-13 | 东莞理工学院 | Novel 2,6-site-substituted BODIPY organic dye sensitizer and preparation method therefor |
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