TTF-Annulated Silicon Phthalocyanine Oligomers and Their External-Stimuli-Responsive Orientational Ordering
TTF-Annulated Silicon Phthalocyanine Oligomers and Their External-Stimuli-Responsive Orientational Ordering
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TTF环化硅酞菁低聚物及其外部刺激响应性取向有序化
DOI：
10.1002/anie.202011025
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
and S. Shimizu
中科院分区：
文献类型：
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作者：
Y. Shiina;Y. Kage;K. Furukawa;H. Wang;H. Yoshikawa;H. Furuta;N. Kobayashi;and S. Shimizu
功能分子的定向控制对于创造自然界中所见的复杂功能至关重要;然而，这种人工系统仍然具有挑战性。在此，我们已经成功地控制了μ-氧代硅酞菁（SiPc）低聚物的旋转异构性，以实现利用四硫富瓦烯（TTF）的分子间相互作用的外部刺激响应取向有序。在该系统中，三种取向模式，自由旋转，重叠构象和交错构象，响应于TTF的氧化态而相互转换，这使得相互作用从由于形成混合价TTF二聚体而导致的缔合到由于TTF二聚体之间的静电排斥而导致的解离。此外，低聚物作为锂离子电池中的阴极材料的稳定性能证明了SiPc低聚物的一维堆叠的可旋转结构可用于控制功能分子朝向分子电子器件的取向。
Orientational control of functional molecules is essential to create complex functionalities as seen in nature; however, such artificial systems have remained challenge. Herein, we have succeeded in controlling rotational isomerism of μ‐oxo silicon phthalocyanine (SiPc) oligomers to achieve an external‐stimuli‐responsive orientational ordering using intermolecular interactions of tetrathiafulvalene (TTF). In this system, three modes of orientations, free rotation, eclipsed conformation, and staggered conformation, were interconverted in response to the oxidation states of TTF, which varied interactions from association due to formation of mixed‐valence TTF dimer to dissociation due to electrostatic repulsion between TTF dications. Furthermore, a stable performance of oligomers as a cathode material in a Li‐ion battery proved that the one‐dimensionally stacked, rotatable structure of SiPc oligomers is useful to control the orientation of functional molecules toward molecular electronics.