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

Arcís-Castillo, Zulema; Muñoz-Lara, Francisco J.; Muñoz, M. Carmen; Aravena, Daniel; Gaspar, Ana B.; Sánchez-Royo, Juan F.; Ruiz, Eliseo; Ohba, Masaaki; Matsuda, Ryotaro; Kitagawa, Susumu; Real, José A.

Abstract

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-desorption 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]}·nSO2 (n ≈ 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 PtII ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination slightly stabilizes the low-spin state of the FeII ions shifting the critical temperatures of the spin transition by 8-12 K. DFT calculations have been performed to rationalize these observations. © 2013 American Chemical Society.

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Título según SCOPUS: Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer
Título de la Revista: INORGANIC CHEMISTRY
Volumen: 52
Número: 21
Editorial: AMER CHEMICAL SOC
Fecha de publicación: 2013
Página de inicio: 12777
Página final: 12783
Idioma: English
DOI:

10.1021/ic4020477

Notas: SCOPUS - SCOPUS