Unité de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium.
Phys Chem Chem Phys. 2010 Oct 28;12(40):13144-52. doi: 10.1039/c0cp00400f. Epub 2010 Sep 14.
Using ab initio tools, we investigate the structural and electronic properties as well as the NMR spectra of hybrid dithienylethene-naphthopyran photochromes synthesised by Frigoli and Mehl (Angew. Chem. Int. Ed., 2005, 44, 5048). All possible closed/open structures have been considered and in each case several conformers could be characterised. Both UV/vis and NMR spectroscopic signatures have been compared to experimental references, and it was shown that the selected DFT/TD-DFT procedure is adequate not only to reproduce the measured spectral values but also to explain the observed photochromic pathways. Our work indicates that several conformers with different relative dithienylethene and naphthopyran orientations might be present experimentally.
利用从头算工具，我们研究了由 Frigoli 和 Mehl 合成的杂二噻烯-萘并吡喃光致变色体的结构和电子性质以及 NMR 谱（Angew. Chem. Int. Ed.，2005，44，5048）。考虑了所有可能的闭环/开环结构，并且在每种情况下都可以对几个构象进行表征。比较了 UV/vis 和 NMR 光谱特征与实验参考值，结果表明所选的 DFT/TD-DFT 程序不仅足以重现测量的光谱值，而且还可以解释观察到的光致变色途径。我们的工作表明，实验中可能存在具有不同相对二噻烯和萘并吡喃取向的几个构象。
