Aronica Christophe, Venancio-Marques Anna, Chauvin Jérôme, Robert Vincent, Lemercier Gilles
Université de Lyon, Laboratoire de Chimie, ENS-Lyon, CNRS, 46, Allée d'Italie, 69364 Lyon Cedex 07, France.
Chemistry. 2009;15(20):5047-55. doi: 10.1002/chem.200802325.
The synthesis and optical properties of 4,5-disubstituted (tert-butyldimethylsilyloxy)-protected catechol derivatives are reported. One or two carbon-carbon triple bond functions were introduced through the Sonogashira cross-coupling reaction. The effects on the optical properties of monosubstitution at the 4-position or disubstitution at the 4- and 5-positions of these catechol derivatives with electron-withdrawing or -donating substituents have been investigated. The experimental chemical-structure-polarisability relationship has been studied by using the Lippert-Mataga correlation and compared with the results of a theoretical study carried out with DFT calculations. These compounds are promising candidates for the fine-tuning of internal charge transfer, but also as potential non-linear chromophores and ligands within multifunctional coordination complexes.
报道了4,5-二取代（叔丁基二甲基硅氧基）保护的儿茶酚衍生物的合成及其光学性质。通过Sonogashira交叉偶联反应引入了一个或两个碳-碳三键官能团。研究了这些儿茶酚衍生物在4位单取代或4位和5位双取代时，吸电子或供电子取代基对其光学性质的影响。利用Lippert-Mataga相关性研究了实验化学结构-极化率关系，并与密度泛函理论（DFT）计算的理论研究结果进行了比较。这些化合物有望用于精细调节内电荷转移，也可作为多功能配位络合物中的潜在非线性发色团和配体。
