Herder Jordan A, Kruse Samantha J, Nicholas Aaron D, Forbes Tori Z, Walter Eric D, Cho Herman, Cahill Christopher L
Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, District of Columbia 20052, United States.
Department of Chemistry, University of Iowa, Chemistry Building W374, Iowa City, Iowa 55242, United States.
Inorg Chem. 2024 Mar 18;63(11):4957-4971. doi: 10.1021/acs.inorgchem.3c04144. Epub 2024 Mar 4.
Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UOCl] bearing compounds containing substituted 1,1'-dialkyl-4,4'-bipyridinum dications (i.e., viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. This reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from [UOCl] to the viologen species. This behavior is elucidated using electron paramagnetic resonance (EPR) spectroscopy and further probed through a series of characterization and computational techniques including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work provides a systematic study of the photoreactivity of the uranyl unit in the solid state, an under-described aspect of fundamental uranyl chemistry.
报道了三种新型含[UOCl]的化合物的合成、结构表征及发光性质，这些化合物含有取代的1,1'-二烷基-4,4'-联吡啶二价阳离子（即紫精）。这些化合物在紫外辐射下会发生光致发光猝灭。这种反应性与两种现象同时发生：四氯铀酰阴离子的自由基化以及光电子转移到紫精，这构成了从[UOCl]到紫精物种的一个电子的形式转移。利用电子顺磁共振（EPR）光谱对这种行为进行了阐释，并通过一系列表征和计算技术进一步探究，包括雷姆 - 韦勒分析、含时密度泛函理论（TD - DFT）和态密度（DOS）。这项工作对固态铀酰单元的光反应性进行了系统研究，这是铀酰基础化学中一个描述不足的方面。
