Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules

Paulo S. Costa; Guanhua Hao; Alpha T. N'Diaye; Lucie Routaboul; Pierre Braunstein; Xin Zhang; Jian Zhang; Thilini K. Ekanayaka; Qin Yin Shi; Vicki Schlegel; Bernard Doudin; Axel Enders; P. A. Dowben

doi:10.1088/1361-648X/ab468c

Manipulation of the molecular spin crossover transition of Fe(H₂B(pz)₂)₂(bipy) by addition of polar molecules

Paulo S. Costa, Guanhua Hao, Alpha T. N'Diaye, Lucie Routaboul, Pierre Braunstein, Xin Zhang, Jian Zhang, Thilini K. Ekanayaka, Qin Yin Shi, Vicki Schlegel, Bernard Doudin, Axel Enders, P. A. Dowben

Food Science and Technology

Research output: Contribution to journal › Article

Abstract

The addition of various dipolar molecules is shown to affect the temperature dependence of the spin state occupancy of the much studied spin crossover Fe(II) complex, [Fe{H₂B(pz)₂}₂(bipy)] (pz = pyrazol-1-yl, bipy = 2,2′-bipyridine). Specifically, the addition of benzimidazole results in a re-entrant spin crossover transition, i.e. the spin state starts in the mostly low spin state, then high spin state occupancy increases, and finally the high spin state occupancy decreases with increasing temperature. This behavior contrasts with that observed when the highly polar p -benzoquinonemonoimine zwitterion C₆H₂(..NH₂)₂(..O)₂ was mixed with [Fe{H₂B(pz)₂}₂(bipy)], which resulted in locking [Fe{H₂B(pz)₂}₂(bipy)] largely into a low spin state while addition of the ethyl derivative C₆H₂(..NHC₂H₅)₂(..O)₂ did not appear to perturb the spin crossover transition of [Fe{H₂B(pz)₂}₂(bipy)].

Original language	English (US)
Article number	034001
Journal	Journal of Physics Condensed Matter
Volume	32
Issue number	3
DOIs	https://doi.org/10.1088/1361-648X/ab468c
State	Published - 2020

Keywords

X-ray absorption spectroscopy
dipolar heteromolecular molecular interactions
re-entrant transition
spin crossover metal organic molecules

ASJC Scopus subject areas

Materials Science(all)
Condensed Matter Physics

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Costa, P. S., Hao, G., N'Diaye, A. T., Routaboul, L., Braunstein, P., Zhang, X., Zhang, J., Ekanayaka, T. K., Shi, Q. Y., Schlegel, V., Doudin, B., Enders, A., & Dowben, P. A. (2020). Manipulation of the molecular spin crossover transition of Fe(H₂B(pz)₂)₂(bipy) by addition of polar molecules. Journal of Physics Condensed Matter, 32(3), [034001]. https://doi.org/10.1088/1361-648X/ab468c

Manipulation of the molecular spin crossover transition of Fe(H₂B(pz)₂)₂(bipy) by addition of polar molecules. / Costa, Paulo S.; Hao, Guanhua; N'Diaye, Alpha T.; Routaboul, Lucie; Braunstein, Pierre; Zhang, Xin; Zhang, Jian; Ekanayaka, Thilini K.; Shi, Qin Yin; Schlegel, Vicki; Doudin, Bernard; Enders, Axel; Dowben, P. A.

In: Journal of Physics Condensed Matter, Vol. 32, No. 3, 034001, 2020.

Research output: Contribution to journal › Article

Costa, PS, Hao, G, N'Diaye, AT, Routaboul, L, Braunstein, P, Zhang, X, Zhang, J, Ekanayaka, TK, Shi, QY, Schlegel, V, Doudin, B, Enders, A & Dowben, PA 2020, 'Manipulation of the molecular spin crossover transition of Fe(H₂B(pz)₂)₂(bipy) by addition of polar molecules', Journal of Physics Condensed Matter, vol. 32, no. 3, 034001. https://doi.org/10.1088/1361-648X/ab468c

Costa, Paulo S. ; Hao, Guanhua ; N'Diaye, Alpha T. ; Routaboul, Lucie ; Braunstein, Pierre ; Zhang, Xin ; Zhang, Jian ; Ekanayaka, Thilini K. ; Shi, Qin Yin ; Schlegel, Vicki ; Doudin, Bernard ; Enders, Axel ; Dowben, P. A. / Manipulation of the molecular spin crossover transition of Fe(H₂B(pz)₂)₂(bipy) by addition of polar molecules. In: Journal of Physics Condensed Matter. 2020 ; Vol. 32, No. 3.

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abstract = "The addition of various dipolar molecules is shown to affect the temperature dependence of the spin state occupancy of the much studied spin crossover Fe(II) complex, [Fe{H2B(pz)2}2(bipy)] (pz = pyrazol-1-yl, bipy = 2,2′-bipyridine). Specifically, the addition of benzimidazole results in a re-entrant spin crossover transition, i.e. the spin state starts in the mostly low spin state, then high spin state occupancy increases, and finally the high spin state occupancy decreases with increasing temperature. This behavior contrasts with that observed when the highly polar p -benzoquinonemonoimine zwitterion C6H2(..NH2)2(..O)2 was mixed with [Fe{H2B(pz)2}2(bipy)], which resulted in locking [Fe{H2B(pz)2}2(bipy)] largely into a low spin state while addition of the ethyl derivative C6H2(..NHC2H5)2(..O)2 did not appear to perturb the spin crossover transition of [Fe{H2B(pz)2}2(bipy)].",

keywords = "X-ray absorption spectroscopy, dipolar heteromolecular molecular interactions, re-entrant transition, spin crossover metal organic molecules",

author = "Costa, {Paulo S.} and Guanhua Hao and N'Diaye, {Alpha T.} and Lucie Routaboul and Pierre Braunstein and Xin Zhang and Jian Zhang and Ekanayaka, {Thilini K.} and Shi, {Qin Yin} and Vicki Schlegel and Bernard Doudin and Axel Enders and Dowben, {P. A.}",

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T1 - Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules

AU - Costa, Paulo S.

AU - Hao, Guanhua

AU - N'Diaye, Alpha T.

AU - Routaboul, Lucie

AU - Braunstein, Pierre

AU - Zhang, Xin

AU - Zhang, Jian

AU - Ekanayaka, Thilini K.

AU - Shi, Qin Yin

AU - Schlegel, Vicki

AU - Doudin, Bernard

AU - Enders, Axel

AU - Dowben, P. A.

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AB - The addition of various dipolar molecules is shown to affect the temperature dependence of the spin state occupancy of the much studied spin crossover Fe(II) complex, [Fe{H2B(pz)2}2(bipy)] (pz = pyrazol-1-yl, bipy = 2,2′-bipyridine). Specifically, the addition of benzimidazole results in a re-entrant spin crossover transition, i.e. the spin state starts in the mostly low spin state, then high spin state occupancy increases, and finally the high spin state occupancy decreases with increasing temperature. This behavior contrasts with that observed when the highly polar p -benzoquinonemonoimine zwitterion C6H2(..NH2)2(..O)2 was mixed with [Fe{H2B(pz)2}2(bipy)], which resulted in locking [Fe{H2B(pz)2}2(bipy)] largely into a low spin state while addition of the ethyl derivative C6H2(..NHC2H5)2(..O)2 did not appear to perturb the spin crossover transition of [Fe{H2B(pz)2}2(bipy)].

KW - X-ray absorption spectroscopy

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