Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Department of Chemistry and Pharmacy and Interdisciplinary Center of Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany.
J Am Chem Soc. 2023 Jul 5;145(26):14190-14195. doi: 10.1021/jacs.3c03486. Epub 2023 Jun 13.
Several dumbbell conjugates featuring MN@-C (M = Sc, Y) and C were prepared to systematically investigate interfullerene electronic interactions and excited state dynamics. From electrochemical investigations, we concluded that the redox potentials of our MN@-C (M = Sc, Y) dumbbells depend largely on the interfullerene electronic interactions. Assisted by DFT calculation, the unique role of metal atoms was highlighted. Most importantly, ultrafast spectroscopy experiments revealed symmetry-breaking charge separation in ScN@C-dumbbell to yield an unprecedented (ScN@C)-(ScN@C) charge separated state. This is, to the best of our knowledge, the first time that symmetry-breaking charge separation following photoexcitation is corroborated in a fullerene system. As such, our work shed light on the significance of interfullerene electronic interactions and their uniqueness for modulating excited state properties.
几种哑铃状配合物，其特征为 MN@-C（M=Sc，Y）和 C，被制备出来以系统地研究富勒烯间的电子相互作用和激发态动力学。通过电化学研究，我们得出结论，我们的 MN@-C（M=Sc，Y）哑铃状配合物的氧化还原电位在很大程度上取决于富勒烯间的电子相互作用。借助密度泛函理论（DFT）计算，突出了金属原子的独特作用。最重要的是，超快光谱实验揭示了 ScN@C-哑铃状配合物中的对称性破缺电荷分离，产生了前所未有的（ScN@C）-（ScN@C）电荷分离态。据我们所知，这是首次在富勒烯体系中证实光激发后对称性破缺的电荷分离。因此，我们的工作阐明了富勒烯间电子相互作用的重要性及其独特性，以调节激发态性质。
