Omomo Satoshi, Tsuji Yukihiro, Sugiura Kenichi, Higashino Tomohiro, Nakano Haruyuki, Imahori Hiroshi, Matano Yoshihiro
Department of Fundamental Sciences, Graduate School of Science and Technology, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Chempluschem. 2017 May;82(5):695-704. doi: 10.1002/cplu.201700051. Epub 2017 Feb 24.
The first examples of unsymmetrical β-substituted donor-π-acceptor (D-π-A)-type 5,15-diazaporphyrin (DAP) sensitizers with both p-aminophenyl and p-carboxyphenyl groups at their peripheral 3-, 7-, 13-, and/or 17-positions have been synthesized for use in dye-sensitized solar cells (DSSCs). UV/Vis absorption and emission spectroscopy, electrochemical measurements, and DFT calculations revealed that these D-π-A dyes exhibit high light-harvesting properties over the whole visible range because of the intrinsic charge-transfer character of their electronic transitions. The cell performances of TiO -based DSSCs fabricated with the newly prepared DAP derivatives were evaluated under standard AM1.5 conditions. Among the four dyes examined, 13,17-bis(p-carboxyphenyl)-3,7-bis[p-(N,N-dimethylamino)phenyl]-DAP showed the highest power conversion efficiency (2.0 %), which was 20 times larger than that obtained with 3-(p-carboxyphenyl)-DAP. These results show that the DAP chromophore could be used as the electron-accepting π unit in various types of functional dyes.
首个不对称β-取代供体-π-受体（D-π-A）型5,15-二氮杂卟啉（DAP）敏化剂已被合成，其在周边3-、7-、13-和/或17-位带有对氨基苯基和对羧基苯基，用于染料敏化太阳能电池（DSSC）。紫外/可见吸收和发射光谱、电化学测量以及密度泛函理论（DFT）计算表明，由于这些D-π-A染料电子跃迁的固有电荷转移特性，它们在整个可见光范围内展现出高光捕获性能。在标准AM1.5条件下评估了用新制备的DAP衍生物制备的基于TiO₂的DSSC的电池性能。在所研究的四种染料中，13,17-双（对羧基苯基）-3,7-双[对-（N,N-二甲基氨基）苯基]-DAP显示出最高的功率转换效率（2.0%），这比用3-（对羧基苯基）-DAP获得的效率大20倍。这些结果表明，DAP发色团可作为各种功能染料中的电子接受π单元。
