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

doi:10.1021/ic4020477

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

Inorganic and Analytical Chemistry

Research output: Contribution to journal › Article › peer-review

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 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.

Original language	English
Pages (from-to)	12777-12783
Number of pages	7
Journal	Inorganic chemistry
Volume	52
Issue number	21
DOIs	https://doi.org/10.1021/ic4020477
Publication status	Published - Nov 4 2013

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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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.

In: Inorganic chemistry, Vol. 52, No. 21, 04.11.2013, p. 12777-12783.

Research output: Contribution to journal › Article › peer-review

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. / Reversible chemisorption of sulfur dioxide in a spin crossover porous coordination polymer. In: Inorganic chemistry. 2013 ; Vol. 52, No. 21. pp. 12777-12783.

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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) {\AA}. 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.",

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AU - Gaspar, Ana B.

AU - Sánchez-Royo, Juan F.

AU - Ruiz, Eliseo

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AU - Kitagawa, Susumu

AU - Real, José A.

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N2 - 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.

AB - 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.

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