High-Pressure Studies of Abnormal Guest-Dependent Expansion in {[Cu(CO3)2](CH6N3)2}n

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• 作者：Qian Li ; Shourui Li ; Kai Wang ; Jing Liu ; Ke Yang ; Bingbing Liu ; Guangtian Zou ; Bo Zou
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：March 20, 2014
• 年：2014
• 卷：118
• 期：11
• 页码：5848-5853
• 全文大小：444K
• 年卷期：v.118,no.11(March 20, 2014)
• ISSN：1932-7455

文摘

High-pressure guest-dependent behaviors of porous coordination polymer {[Cu(CO₃)₂](CH₆N₃)₂}_n (GCC) are investigated using synchrotron X-ray diffraction (XRD) and Raman techniques. In GCC, the host framework of 3D [Cu(CO₃)₂]^{2鈥?/sup> coordination network presents a diamond-like topology, with guest guanidinium cations locating at the window of the pores through N鈥揌路路路O hydrogen bonds. Above a critical pressure, the external force can squeeze the guanidinium ions into the pores, leading to the abnormal expansion of the structure. Meanwhile, the critical pressure for expansion can be effectively lowered when no pressure transmitting medium is employed. Moreover, nonhydrostatic effects can promote the insertion of guanidinium ions, along with the amorphization of the structure, and thus affect the reversibility of the structure after releasing the pressure. Our results show that pressure is an effective tool to tune the host鈥揼uest relationship and to prepare high-pressure phase host鈥揼uest materials. Meanwhile, this study broadens the understanding of host鈥揼uest chemistry and offers a new strategy for fabricating novel materials with applications of pressure switches and zero contraction material in porous coordination polymers.}