Integration of Intrinsic Proton Conduction and Guest-Accessible Nanospace into a Coordination Polymer

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• 作者：Daiki Umeyama ; Satoshi Horike ; Munehiro Inukai ; Susumu Kitagawa
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 31, 2013
• 年：2013
• 卷：135
• 期：30
• 页码：11345-11350
• 全文大小：287K
• 年卷期：v.135,no.30(July 31, 2013)
• ISSN：1520-5126

文摘

We report the synthesis and characterization of a coordination polymer that exhibits both intrinsic proton conductivity and gas adsorption. The coordination polymer, consisting of zinc ions, benzimidazole, and orthophosphate, exhibits a degree of flexibility in that it adopts different structures before and after dehydration. The dehydrated form shows higher intrinsic proton conductivity than the original form, reaching as high as 1.3 脳 10^鈥? S cm^鈥? at 120 掳C. We found that the rearranged conduction path and liquid-like behavior of benzimidazole molecules in the channel of the framework afforded the high proton conductivity. Of the two forms of the framework, only the dehydrated form is porous to methanol and demonstrates guest-accessible space in the structure. The proton conductivity of the dehydrated form increases by 24 times as a result of the in situ adsorption of methanol molecules, demonstrating the dual functionality of the framework. NMR studies revealed a hydrogen-bond interaction between the framework and methanol, which enables the modulation of proton conductivity within the framework.