Zhao Yu, Zhang Yuchen, Wang Tao, Pei Runbo, Zhao Yue, Xue Xiao-Song, Wang Xinping
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2024 Dec 9;63(50):e202411180. doi: 10.1002/anie.202411180. Epub 2024 Oct 22.
This work reports synthesis of a germylene based donor-acceptor molecule and its thermal excitation to a triplet state by coordination with a Lewis acid. Products have been characterized by single crystal X-ray diffraction, EPR spectroscopy, and SQUID measurement, in conjunction with DFT calculation. The singlet-triplet energy gap of the donor-acceptor molecule is dramatically reduced from -18.8 to -7.2 kcal/mol by the coordination with B(CF) (BCF), which enables an intramolecular single electron transfer from one germylene moiety to another upon heating, forming an intramolecular radical ion pair with diradical character. The work provides an approach to the formation of thermally populated open-shell species of heavier main group elements.
这项工作报道了一种基于亚锗烯的给体-受体分子的合成及其通过与路易斯酸配位热激发至三重态的过程。产物已通过单晶X射线衍射、电子顺磁共振光谱和超导量子干涉仪测量，并结合密度泛函理论计算进行了表征。通过与B(CF)（BCF）配位，给体-受体分子的单重态-三重态能隙从-18.8大幅降低至-7.2 kcal/mol，这使得加热时分子内从一个亚锗烯部分到另一个亚锗烯部分发生单电子转移，形成具有双自由基特征的分子内自由基离子对。这项工作提供了一种形成热填充的较重主族元素开壳层物种的方法。
