Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, P R China.
Phys Chem Chem Phys. 2012 Sep 7;14(33):11743-52. doi: 10.1039/c2cp41952a. Epub 2012 Jul 25.
A series of bis(arylidene)cycloalkanone compounds based on cyclobutanone, cyclopentanone, cyclohexanone and cycloheptanone, C4-C7, respectively, with a D-π-A-π-D structure containing the same donor and acceptor but different alicyclic rings was prepared. The effects of alicyclic ring size on the photophysical, photochemical and electrochemical properties of these compounds were investigated systematically. We found that an increase of the number of carbons in the central alicyclic ring leads to changes in geometry, which has significant effects on the conjugation, and photophysical and photochemical properties. These effects include decreases in the fluorescence quantum yield, transient lifetimes, peak extinction coefficients, and the singlet oxygen quantum yield with the increase of the ring size. The one-photon absorption spectra, the two-photon absorption (2PA) spectra, and the fluorescence spectra all show a hypsochromic shift with increasing ring size. The results of this study provide guidance for the design of new cycloketone-based D-π-A-π-D 2PA compounds for photopolymerization and photodynamic therapy applications.
本文制备了一系列基于环丁酮、环戊酮、环己酮和环庚酮的双（亚芳基）环己烷酮化合物，C4-C7，分别具有相同供体和受体但不同脂环环的 D-π-A-π-D 结构。系统研究了脂环环大小对这些化合物的光物理、光化学和电化学性质的影响。我们发现，中环脂环中环碳原子数的增加会导致几何形状的变化，这对共轭、光物理和光化学性质有显著影响。这些影响包括荧光量子产率、瞬态寿命、峰值消光系数和单线态氧量子产率随环尺寸的增加而降低。单光子吸收光谱、双光子吸收（2PA）光谱和荧光光谱均随环尺寸的增加而呈现蓝移。本研究结果为设计用于光聚合和光动力治疗应用的新型基于环酮的 D-π-A-π-D 2PA 化合物提供了指导。
