Large‐Amplitude Thermal Vibration‐Coupled Valence Tautomeric Transition Observed in a Conductive One‐Dimensional Rhodium-Dioxolene Complex
Large‐Amplitude Thermal Vibration‐Coupled Valence Tautomeric Transition Observed in a Conductive One‐Dimensional Rhodium-Dioxolene Complex
复制标题
在导电一维铑-二氧杂环戊烯配合物中观察到大振幅热振动耦合价互变异构转变
DOI：
10.1002/chem.202004217
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Akashi Haruo
中科院分区：
文献类型：
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作者：
Mitsumi Minoru;Komatsu Yuuki;Hashimoto Masahiro;Toriumi Koshiro;Kitagawa Yasutaka;Miyazaki Yuji;Akutsu Hiroki;Akashi Haruo
动态分子晶体是材料科学的基础科学，在分子器件方面具有潜在的应用价值，因此对其的研究一直是材料科学家们关注的热点。本文中，报道了一维（1D）铑-二氧杂环戊烯络合物，其随着相变而表现出性质的急剧变化。X射线光电子能谱（XPS）显示室温（RT）相处于混合价态，因此，剧烈变化源于RT相中出现的混合价态。另一个值得注意的特征是铑原子沿着一维链的均方位移在RT相中显著增加，表明Rh−Rh键的大振幅振动。根据这些结果，提出了RT相中混合价态出现的可能机制，该机制基于从1D d带到半醌π* 轨道的热电子转移以及Rh−Rh键的大振幅振动。
The exploration of dynamic molecular crystals is a fascinating theme for materials scientists owing to their fundamental science and potential application to molecular devices. Herein, a one‐dimensional (1D) rhodium‐dioxolene complex is reported that exhibits drastic changes in properties with the phase transition. X‐ray photoelectron spectroscopy (XPS) revealed that the room‐temperature (RT) phase is in a mixed‐valence state, and therefore, the drastic changes originate from the mixed‐valence state appearing in the RT phase. Another notable feature is that the mean square displacements of the rhodium atoms along the 1D chain dramatically increased in the RT phase, indicating a large‐amplitude vibration of the Rh−Rh bonds. From these results, a possible mechanism for the appearance of the mixed‐valence state in the RT phase was proposed based on the thermal electron transfer from the 1D d‐band to the semiquinonato π* orbital coupled with the large‐amplitude vibration of the Rh−Rh bonds.