Anionic clay surface facilitates electron transfer between an excited donor encapsulated within a cationic capsule and a cationic electron acceptor

Natsuki Morita , A. Mohan Raj , Takuya Fujimura , Tetsuya Shimada , Vaidhyanathan Ramamurthy , Shinsuke Takagi
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Abstract

Fluorescence quenching of an excited guest encapsulated within a cationic host by a cationic molecule was examined on an anionic inorganic surface. Repulsion between the host and the quencher was overcome by adsorbing both an anionic surface. Dimethyl stilbene (DMS), octa amine (OAm216+), viologen derivatives (VD2+) and saponite are used as guest, cationic capsule, cationic electron acceptor and anionic inorganic surface, respectively. The fluorescence behavior of DMS within OAm216+ (denoted as DMS@OAm216+) was observed by steady-state and time-resolved fluorescence measurements. As a result of electron transfer the fluorescence of DMS@OAm216+ was quenched by VD2+ under the presence of saponite, while no quenching was observed in the absence of saponite. Those results indicate that the dynamic electron transfer between DMS@OAm216+ and VD2+ which are electrostatically repulsive, can be observed in the (DMS@OAm216+)-VD2+-saponite triad supramolecular system where the two cationic systems are brought closer by the anionic clay sheet.

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阴离子粘土表面促进了封装在阳离子胶囊内的受激供体和阳离子电子受体之间的电子转移
在阴离子无机表面上研究了被阳离子分子包裹在阳离子寄主内的激发客体的荧光猝灭。寄主和猝灭剂之间的斥力通过吸附阴离子表面来克服。以二甲基二苯乙烯(DMS)、八胺(OAm216+)、紫素衍生物(VD2+)和皂土分别作为客体、阳离子胶囊、阳离子电子受体和阴离子无机表面。通过稳态和时间分辨荧光测量观察DMS在OAm216+(记为DMS@OAm216+)中的荧光行为。由于电子转移,在皂土存在的情况下,DMS@OAm216+的荧光被VD2+猝灭,而在皂土不存在的情况下,没有观察到猝灭。结果表明,在(DMS@OAm216+)-VD2+-皂土三元超分子体系中,具有静电斥力的DMS@OAm216+和VD2+发生了动态电子转移,其中阴离子粘土片拉近了两个阳离子体系的距离。
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