Lugovik Kseniya I, Eltyshev Alexander K, Benassi Enrico, Belskaya Nataliya P
Ural Federal University, 19 Mira Str., Yekaterinburg, 620002, Russia.
Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy.
Chem Asian J. 2017 Sep 19;12(18):2410-2425. doi: 10.1002/asia.201700721. Epub 2017 Aug 22.
Independent of the substrate structure and reaction conditions, 3-amino-2-cyanothioacrylamides, which contain two active electrophilic centers, were shown to interact with various active halo methylene compounds under mild conditions to afford 5-acyl-2-amino-3-cyanothiophenes as the only products. A series of new polyfunctional thiophene derivatives with a rare combination of functionalities were synthesized, and their photophysical properties were experimentally and computationally investigated. The calculated electronic characteristics of the ground and excited states were compared to the experimental results, which provided a good understanding of the relationship between the optoelectronic properties and the molecular structures. After absorption of light quanta, the systems populate an intramolecular charge-transfer (ICT) Franck-Condon state, and emission occurs from a twisted ICT minimum.
与底物结构和反应条件无关，含有两个活性亲电中心的3-氨基-2-氰基硫代丙烯酰胺在温和条件下能与各种活性卤代亚甲基化合物相互作用，唯一产物是5-酰基-2-氨基-3-氰基噻吩。合成了一系列具有罕见功能组合的新型多功能噻吩衍生物，并通过实验和计算研究了它们的光物理性质。将计算得到的基态和激发态电子特性与实验结果进行比较，这有助于很好地理解光电性质与分子结构之间的关系。吸收光量子后，体系跃迁到分子内电荷转移（ICT）弗兰克-康登态，发射光则来自扭曲ICT最小值态。
