Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer

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

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53 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)12777-12783
Number of pages7
JournalInorganic chemistry
Volume52
Issue number21
DOIs
Publication statusPublished - Nov 4 2013

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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