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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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.

元の言語英語
ページ(範囲)12777-12783
ページ数7
ジャーナルInorganic chemistry
52
発行部数21
DOI
出版物ステータス出版済み - 11 4 2013

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Arcís-Castillo, Z., Muñoz-Lara, F. J., Muñoz, M. C., Aravena, D., Gaspar, A. B., Sánchez-Royo, J. F., Ruiz, E., Ohba, M., Matsuda, R., Kitagawa, S., & Real, J. A. (2013). Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer. Inorganic chemistry, 52(21), 12777-12783. https://doi.org/10.1021/ic4020477