Organic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee-247 667, India.
Chem Asian J. 2012 Dec;7(12):2942-54. doi: 10.1002/asia.201200752. Epub 2012 Sep 28.
Organic dyes that contain a 2,7-diaminofluorene-based donor, a cyanoacrylic-acid acceptor, and various aromatic conjugation segments, which are composed of benzene, fluorene, carbazole, and thiophene units, as a π-bridge have been synthesized and characterized by optical, electrochemical, and theoretical investigations. The trends in the absorption and electrochemical properties of these dyes are in accordance with the electron-donating ability of the conjugating segment. Consequently, the dyes that contained a 2,7-carbazole unit in the π-spacer exhibited red-shifted absorption and lower oxidation potentials than their corresponding fluorene- and phenylene-bridged dyes. However, the enhanced power-conversion efficiency that was exhibited by the fluorene-bridged dyes in the DSSCs was attributed to their broader and intense absorption. Despite the longer-wavelength absorption and reasonable optical density, carbazole-bridged dyes exhibited lower power-conversion efficiencies, which were ascribed to the poor alignment of the LUMO level in these dyes, thereby leading to the inhibition of electron injection into the TiO(2) conduction band.
合成并通过光学、电化学和理论研究对含有基于 2,7-二氨基芴的给体、氰基丙烯酸酯受体和各种芳香共轭片段的有机染料进行了表征,这些片段由苯、芴、咔唑和噻吩单元作为π-桥组成。这些染料的吸收和电化学性质的趋势与共轭片段的供电子能力一致。因此,在π-间隔物中含有 2,7-咔唑单元的染料表现出比其相应的芴桥和亚苯基桥染料红移的吸收和更低的氧化电位。然而,在 DSSC 中,芴桥染料表现出更高的功率转换效率,这归因于它们更宽和更强的吸收。尽管咔唑桥染料具有更长的波长吸收和合理的光密度,但表现出较低的功率转换效率,这归因于这些染料中 LUMO 能级的排列不佳,从而抑制了电子注入 TiO(2)导带。