Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer

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• 作者：Zulema Arc铆s-Castillo ; Francisco J. Mu帽oz-Lara ; M. Carmen Mu帽oz ; Daniel Aravena ; Ana B. Gaspar ; Juan F. S谩nchez-Royo ; Eliseo Ruiz ; Masaaki Ohba ; Ryotaro Matsuda ; Susumu Kitagawa ; Jos茅 A. Real
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：November 4, 2013
• 年：2013
• 卷：52
• 期：21
• 页码：12777-12783
• 全文大小：374K
• 年卷期：v.52,no.21(November 4, 2013)
• ISSN：1520-510X

文摘

The chemisorption of sulfur dioxide (SO₂) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)₄]} has been investigated at room temperature. Thermal analysis and adsorption鈥揹esorption isotherms showed that ca. 1 mol of SO₂ per mol of {Fe(pz)[Pt(CN)₄]} was retained in the pores. Nevertheless, the SO₂ was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)₄]}路nSO₂ (n 鈮?0.25) were grown in water solutions saturated with SO₂, and its crystal structure was analyzed at 120 K. The SO₂ molecule is coordinated to the Pt^II ion through the sulfur atom ion, Pt鈥揝 = 2.585(4) 脜. This coordination slightly stabilizes the low-spin state of the Fe^II ions shifting the critical temperatures of the spin transition by 8鈥?2 K. DFT calculations have been performed to rationalize these observations.