Role of Pyridinium Groups and Iodide Ions in Photoelectrochromism in Viologen-Based Ion-Pair Charge-Transfer Complexes: Molecular Orbital Analysis
Role of Pyridinium Groups and Iodide Ions in Photoelectrochromism in Viologen-Based Ion-Pair Charge-Transfer Complexes: Molecular Orbital Analysis
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DOI：
10.1021/acs.jpcc.7b10281
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发表时间：
2018-02
影响因子：
3.7
通讯作者：
Y. Orimoto;K. Ishimoto;Y. Aoki
中科院分区：
文献类型：
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作者：
Y. Orimoto;K. Ishimoto;Y. Aoki
通过量子化学计算，研究了紫外光(V)基离子对电荷转移配合物中光致电子转移（ET）的基本原理，以及由此产生的光电致变色与光电开关应用的关系。为此，建立了反阴离子对光致紫外或联苯（BP）衍生物的光致ET模型，并分析了其与结构的关系。我们的研究结果表明，假设光致ET， V2+的电子还原，即V2+→V+→V0，由于V2+的最低未占据分子轨道（LUMO）呈现平面倾向，使其构象偏好从扭曲结构转变为平面结构。中性BP的还原也出现了类似的特征，即BP0→BP -→BP2 -，由于BP0中的LUMO导致了扭曲→平面的偏好变化。V2+和BP0之间的相似性可以用它们相似的MO形状和相同的电子数来解释。时变密度泛函理论(…
Quantum chemistry calculations were performed to examine the fundamentals of photoinduced electron transfer (ET) in viologen (V)-based ion-pair charge-transfer complexes and the resulting photoelectrochromism with respect to photoswitching applications. For the purpose, the photoinduced ET from counter anions to viologen or biphenyl (BP) derivatives was modeled, and its relationship with their structures was analyzed. Our results showed that the electron reduction of V2+, assuming photoinduced ET, that is, V2+ → V+ → V0, changes the conformational preference from a twisted to a planar structure because of the lowest unoccupied molecular orbital (LUMO) in V2+ showing a planar tendency. A similar feature appears in the reduction of neutral BP, that is, BP0 → BP– → BP2–, leading to a twisted → planar preference change because of the LUMO in BP0. The similarity between V2+ and BP0 can be explained by their similar MO shape and their identical number of electrons. The time-dependent density functional theory (...