Department of Chemistry, PhotoGreen Lab, Viale Taramelli 12, 27100, Pavia, Italy.
Stratingh Institute for Chemistry, Center for Systems Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Photochem Photobiol Sci. 2022 May;21(5):667-685. doi: 10.1007/s43630-021-00119-6. Epub 2021 Nov 13.
The photochemistry of aryl chlorides having a X-SiMe group (X = O, NR, S, SiMe) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable ϭ,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl-chlorine bond and homolysis of the X-silicon bond. The former path is found in chlorinated phenols and anilines, whereas the latter is exclusive in the case of silylated thiophenols and aryl silanes. A combined experimental/computational approach was pursued to explain such a photochemical behavior.Graphical abstract.
已详细研究了芳基氯的光化学性质，这些芳基氯具有连接在芳环上的 X-SiMe 基团（X=O、NR、S、SiMe），目的是生成有价值的 ϭ、π-杂二自由基。从芳烃的激发三重态中观察到两种竞争途径，即芳基-氯键的异裂和 X-硅键的均裂。前一种途径存在于氯化苯酚和苯胺中，而后者则在硅烷化噻吩酚和芳基硅烷中是独特的。采用实验/计算相结合的方法来解释这种光化学行为。
