Liu Zhichang, Frasconi Marco, Liu Wei-Guang, Zhang Yu, Dyar Scott M, Shen Dengke, Sarjeant Amy A, Goddard William A, Wasielewski Michael R, Stoddart J Fraser
Institute of Natural Sciences, Westlake Institute for Advanced Study , Westlake University , 18 Shilongshan Road , Hangzhou 310024 , China.
Department of Chemical Sciences , University of Padova , Via Marzolo 1 , Padova 35131 , Italy.
J Am Chem Soc. 2018 Aug 1;140(30):9387-9391. doi: 10.1021/jacs.8b05322. Epub 2018 Jul 17.
Herein, we report an unprecedented mixed-valence crystal superstructure that consists of a 2:1 host-guest complex [MV⊂(CBPQT)] [MV = methyl viologen, CBPQT = cyclobis(paraquat- p-phenylene)]. One electron is distributed statistically between three [MV⊂(CBPQT)] composed of a total of 15 viologen units. The mixed-valence state is validated by single-crystal X-ray crystallography, which supports an empirical formula of [MV⊂(CBPQT)]·(PF) for the body-centered cubic superstructure. Electron paramagnetic resonance provides further evidence of electron delocalization. Quantum chemistry calculations confirm the mixed-valence state in the crystal superstructure. Our findings demonstrate that precise tuning of the redox states in host-guest systems can lead to a promising supramolecular strategy for achieving long-range electron delocalization in solid-state devices.
在此，我们报道了一种前所未有的混合价晶体超结构，它由2:1的主客体复合物[MV⊂(CBPQT)]组成[MV = 甲基紫精，CBPQT = 环双(对苯撑二甲基联吡啶)]。一个电子统计分布在由总共15个紫精单元组成的三个[MV⊂(CBPQT)]之间。混合价态通过单晶X射线晶体学得到验证，该晶体学支持体心立方超结构的经验式为[MV⊂(CBPQT)]·(PF)。电子顺磁共振提供了电子离域的进一步证据。量子化学计算证实了晶体超结构中的混合价态。我们的发现表明，主客体体系中氧化还原态的精确调控可导致一种有前景的超分子策略，用于在固态器件中实现长程电子离域。
