Structural Flexibilities and Gas Adsorption Properties of One-Dimensional Copper(II) Polymers with Paddle-Wheel Units by Modification of Benzoate Ligands

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• 作者：Kiyonori Takahashi ; Norihisa Hoshino ; Takashi Takeda ; Shin-ichiro Noro ; Takayoshi Nakamura ; Sadamu Takeda ; Tomoyuki Akutagawa
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 5, 2015
• 年：2015
• 卷：54
• 期：19
• 页码：9423-9431
• 全文大小：673K
• ISSN：1520-510X

文摘

CO₂ and N₂ gas adsorption/desorption properties of one-dimensional copper(II) polymers with paddle-wheel units [Cu^II₂(p-XBA)₄(pyrazine)]_鈭?/i> were successfully controlled through the tuning of interchain interactions by modification of para-substituent X groups on the benzoate (BA) ligands (X = Cl, Br, I, and OCH₃). Although none of the four crystals had sufficient void space to integrate the crystallization solvents, gate-opening gas adsorption and desorption behaviors coupled with structural phase transitions were observed for CO₂ (T = 195 K) and N₂ (T = 77 K), with differences depending on the precise substituent. van der Waals interchain interactions, specifically 蟺路路路蟺, halogen路路路蟺, and C鈥揌路路路蟺 contacts, were dominant in forming the crystal lattice; their magnitude was associated with gate-opening pressure and hysteresis behaviors. Both the type and magnitude of the interactions were evaluated by Hirshfeld surface analysis, which indicated that structural flexibility decreased as larger halogen atoms were included. Overall, weak interchain interaction and structural flexibility generated new void spaces to adsorb CO₂ and N₂ gases.