title: Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer.
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 Pt(II) ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination slightly stabilizes the low-spin state of the Fe(II) ions shifting the critical temperatures of the spin transition by 8-12 K. DFT calculations have been performed to rationalize these observations.
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia , 46980 Paterna, Valencia, Spain.
authors.forename: Zulema
authors.initials: Z
authors.lastname: Arcís-Castillo
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Muñoz-Lara
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Muñoz
authors.forename: Daniel
authors.initials: D
authors.lastname: Aravena
authors.forename: Ana B
authors.initials: AB
authors.lastname: Gaspar
authors.forename: Juan F
authors.initials: JF
authors.lastname: Sánchez-Royo
authors.forename: Eliseo
authors.initials: E
authors.lastname: Ruiz
authors.forename: Masaaki
authors.initials: M
authors.lastname: Ohba
authors.forename: Ryotaro
authors.initials: R
authors.lastname: Matsuda
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa
authors.forename: José A
authors.initials: JA
authors.lastname: Real
mesh_terms: D000327:Adsorption; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D015394:Molecular Structure; D013458:Sulfur Dioxide / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D013458:Sulfur Dioxide