Faries Kaitlyn M, Diers James R, Springer Joseph W, Yang Eunkyung, Ptaszek Marcin, Lahaye Dorothée, Krayer Michael, Taniguchi Masahiko, Kirmaier Christine, Lindsey Jonathan S, Bocian David F, Holten Dewey
†Department of Chemistry, Washington University, St. Louis, Missouri 63130-4889, United States.
‡Department of Chemistry, University of California, Riverside, Riverside, California 92521-0403, United States.
J Phys Chem B. 2015 Jun 18;119(24):7503-15. doi: 10.1021/jp511257w. Epub 2015 Jan 14.
Efficient light harvesting for molecular-based solar-conversion systems requires absorbers that span the photon-rich red and near-infrared (NIR) regions of the solar spectrum. Reported herein are the photophysical properties of a set of six chlorin-imides and nine synthetic chlorin analogues that extend the absorption deeper (624-714 nm) into these key spectral regions. These absorbers help bridge the gap between typical chlorins and bacteriochlorins. The new compounds have high fluorescence quantum yields (0.15-0.34) and long singlet excited-state lifetimes (4.2-10.9 ns). The bathochromic shift in Qy absorption is driven by substituent-based stabilization of the lowest unoccupied molecular orbital, with the largest shifts for chlorins that bear an electron-withdrawing, conjugative group at the 3-position in combination with a 13,15-imide ring.
基于分子的太阳能转换系统实现高效的光捕获需要能覆盖太阳光谱中富含光子的红色和近红外（NIR）区域的吸收剂。本文报道了一组六种二氢卟吩酰亚胺和九种合成二氢卟吩类似物的光物理性质，这些物质将吸收范围更深地（624 - 714 nm）扩展到这些关键光谱区域。这些吸收剂有助于弥合典型二氢卟吩和细菌叶绿素之间的差距。新化合物具有高荧光量子产率（0.15 - 0.34）和长单重激发态寿命（4.2 - 10.9 ns）。Qy吸收中的红移是由基于取代基的最低未占分子轨道的稳定作用驱动的，对于在3位带有吸电子共轭基团并结合13,15 - 酰亚胺环的二氢卟吩，红移最大。
