Two-Dimensional Charge-Separated Metal鈥揙rganic Framework for Hysteretic and Modulated Sorption

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• 作者：Sujuan Wang ; Qiuli Yang ; Jianyong Zhang ; Xuepeng Zhang ; Cunyuan Zhao ; Long Jiang ; Cheng-Yong Su
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 15, 2013
• 年：2013
• 卷：52
• 期：8
• 页码：4198-4204
• 全文大小：421K
• 年卷期：v.52,no.8(April 15, 2013)
• ISSN：1520-510X

文摘

A charge-separated metal鈥搊rganic framework (MOF) has been successfully synthesized from an imidazolium tricarboxylate ligand, N-(3,5-dicarboxylphenyl)-N鈥?(4-carboxylbenzyl)imidazolium chloride (DCPCBImH₃Cl), and a zinc(II) dimeric secondary building unit, namely, DCPCBim-MOF-Zn, which shows an unprecedented 3,6-connected two-dimensional net topology with the point (Schl盲fli) symbol (4².6)₂(4⁴.6⁹.8²). The framework contains one-dimensional highly polar channels, and density functional theory calculations show that positive charges are located on the imidazolium/phenyl rings and negative charges on the carboxylate moieties. The charge-separated nature of the pore surface has a profound effect in their adsorption behavior, resulting in remarkable hysteretic sorption of various gases and vapors. For CO₂, the hysteretic sorption was observed to occur even up to 298 K. Additionally, trace chloride anions present in the pore channels are able to modulate the gas-sorption behavior.