Molecular Wires with Controllable π-Delocalization Incorporating Redox-Triggered π-Conjugated Switching Units
Molecular Wires with Controllable π-Delocalization Incorporating Redox-Triggered π-Conjugated Switching Units
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具有可控 π 离域并结合氧化还原触发 π 共轭开关单元的分子线
DOI：
10.1002/cplu.201800341
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发表时间：
2018
期刊：
影响因子：
3.4
通讯作者：
Suzuki Takanori
中科院分区：
文献类型：
--
作者：
Nojo Wataru;Tamaoki Hitomi;Ishigaki Yusuke;Katoono Ryo;Fujiwara Kenshu;Fukushima Takanori;Suzuki Takanori
全氟联苯- 2,2 ' -二基化及其对应的二氢菲型电子给体在双电子转移时可相互转换。氧化还原触发的C - C键形成/解理引起联苯单元扭转角的剧烈变化。因此，π -离域ON/OFF开关被观察到在电解两个苯乙基的线性扩展类似物时紫外吸收的变化。进一步合成了一个分子长度约为3.5 nm，具有两个开关单元的扩展π -体系。谱图和伏安分析表明，由于在四离子化状态下单元间静电斥力很小，这两个单元几乎同时起作用。因此，该对是具有可控π -离域的“分子线”的一个有希望的开关单元，其中通过合并多个开关单元可以实现更高的离域开/关比。
A perfluorobiphenyl‐2,2′‐diyl dication and its corresponding dihydrophenanthrene‐type electron donor are interconvertible upon two‐electron transfer. Redox‐triggered C−C bond‐formation/cleavage caused a drastic change in the torsion angle of the biphenyl unit. Thus, π‐delocalization ON/OFF switching was observed as a change in the UV absorption upon electrolysis of the linearly extended analogue with two phenylethynyl groups. A further extended π‐system with a molecular length of ca. 3.5 nm, which has two switching units, was synthesized. Spectroelectrograms as well as voltammetric analyses showed that the two units act nearly simultaneously because of the very small inter‐unit electrostatic repulsion in the tetracationic state. Thus, the present pair is a promising candidate as a switching unit for “molecular wires” with controllable π‐delocalization, in which a higher ON/OFF ratio of delocalization could be realized by incorporating multiple switching units.