Yeh Shih-Chieh, Wang Li-Jing, Yang Hong-Ming, Dai Yu-Huei, Lin Chao-Wen, Chen Chin-Ti, Jeng Ru-Jong
Institute of Chemistry, Academia Sinica, 128 Academia Rd., Sec. 2, Taipei, 11529, Taiwan.
Institute of Polymer Science and Engineering, National Taiwan University, 1 Roosevelt Rd., Sec. 4, Taipei, 10617, Taiwan.
Chemistry. 2017 Oct 20;23(59):14747-14759. doi: 10.1002/chem.201702285. Epub 2017 Sep 25.
Seven donor and acceptor 2,6-disubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes have been synthesized and characterized. Including MPBTCA, which is a known compound, the seven BODIPY dyes have been characterized by varied physical methods, such as UV/Visible absorption spectroscopy, low energy photo-electron spectroscopy (AC-2), and HOMO-LUMO DFT/TDDFT calculation. All seven BODIPY dyes have absorption λ around 535-545 nm, which is significantly longer than 499 nm of 4,4-difluoro-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene (PM 546). Having structural variation on donor group, acceptor group, donor π-spacer, acceptor π-spacer, and the substituent on boron, some BODIPY dyes exhibit small extinction coefficients or spectral integrals in solution (MPCtBTCA, MPBT-pyO, MPBTT-pyO, MTBTCA), broadening absorption spectral profile (MTBTCA), weak intramolecular charge transfer characteristics (MPBT-pyO, MPBTT-pyO, MTBTCA), too low LUMO energy level (PPBTCA), or insufficient dye-uptake by TiO FTO (MPBT-pyO, MPBTT-pyO, MTBTCA). Two of the seven BODIPY dyes, MPBTCA and MPBTTCA, do not show the adverse properties like other BODIPY dyes. With our improved TiO FTO (fluorine doped tin oxide) dyeing method, namely a solution dropping method, high performance dye-sensitized solar cells (DSCs) have been realized by MPBTCA and MPBTTCA photosensitizers. Power conversion efficiencies of 6.3 and 6.4 % have been achieved by MPBTCA and MPBTTCA DSCs, respectively. To the best of our knowledge, MPBTCA and MPBTTCA are the most efficient dyes for the donor and acceptor 2,6-disubstituted BODIPY DSCs so far.
已合成并表征了七种供体和受体 2,6 - 二取代的 4,4 - 二氟 - 4 - 硼 - 3a,4a - 二氮杂 - s - 茚(BODIPY)染料。包括已知化合物 MPBTCA 在内,这七种 BODIPY 染料已通过多种物理方法进行了表征,如紫外/可见吸收光谱、低能光电子能谱(AC - 2)以及 HOMO - LUMO DFT/TDDFT 计算。所有七种 BODIPY 染料的吸收波长约为 535 - 545 nm,这明显长于 4,4 - 二氟 - 1,3,5,7,8 - 五甲基 - 4 - 硼 - 3a,4a - 二氮杂 - s - 茚(PM 546)的 499 nm。由于在供体基团、受体基团、供体π - 间隔基、受体π - 间隔基以及硼上的取代基存在结构变化,一些 BODIPY 染料在溶液中表现出小的消光系数或光谱积分(MPCtBTCA、MPBT - pyO、MPBTT - pyO、MTBTCA)、吸收光谱轮廓变宽(MTBTCA)、分子内电荷转移特性较弱(MPBT - pyO、MPBTT - pyO、MTBTCA)、LUMO 能级过低(PPBTCA)或 TiO FTO 对染料的摄取不足(MPBT - pyO、MPBTT - pyO、MTBTCA)。七种 BODIPY 染料中的两种,MPBTCA 和 MPBTTCA,没有表现出像其他 BODIPY 染料那样的不良性质。通过我们改进的 TiO FTO(氟掺杂氧化锡)染色方法,即溶液滴加法,利用 MPBTCA 和 MPBTTCA 光敏剂实现了高性能染料敏化太阳能电池(DSC)。MPBTCA 和 MPBTTCA DSC 的功率转换效率分别达到了 6.3%和 6.4%。据我们所知,MPBTCA 和 MPBTTCA 是迄今为止供体和受体 2,6 - 二取代 BODIPY DSC 中效率最高的染料。