Vibronic model for cooperative spin-crossover in pentanuclear {[M III(CN)6]2[MII(tmphen) 2]3} (M/M= Co/Fe, Fe/Fe) compounds

Sophia Klokishner; Serghei Ostrovsky; Andrei Palii; Michael Shatruk; Kristen Funck; Kim R. Dunbar; Boris Tsukerblat

doi:10.1021/jp207111r

Vibronic model for cooperative spin-crossover in pentanuclear {[M ^III(CN)₆]₂[M^II(tmphen) ₂]₃} (M/M= Co/Fe, Fe/Fe) compounds

Sophia Klokishner, Serghei Ostrovsky, Andrei Palii, Michael Shatruk, Kristen Funck, Kim R. Dunbar, Boris Tsukerblat

Department of Chemistry

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Abstract

In this paper we present a microscopic model for the cooperative spin-crossover (SCO) phenomenon in crystals containing cyano-bridged pentanuclear clusters {[M^III(CN)₆]₂[M ^II(tmphen)₂]₃} (M/M= Co/Fe, 1; Fe/Fe, 2) with a trigonal bipyramidal (TBP) structure. The low-spin to high-spin (ls-hs) transition is considered as a cooperative phenomenon that is driven by the interaction of electronic shells of Fe^II ions with totally symmetric deformation of the local environment that is extended over the crystal lattice via the acoustic phonon field. Due to proximity of Fe^II ions in the cluster, the short-range intracluster interaction between these ions via the optical phonon field is included as well. The model takes into consideration also the spin-orbit coupling operating within the cubic ⁵T ₂(t₂4e²) term of the hs-Fe^II ions. For cluster 2 the Heisenberg-type exchange interaction between the hs-Fe ^II and ls-Fe^III ions is taken into account. The competition between short- and long-range interactions is shown to determine the type and temperature of the SCO transition in cluster systems. The proposed model explains, in a unique way, the temperature dependence of the static magnetic susceptibility and the Mössbauer spectra of the title compounds. The approach described in this paper represents a theoretical tool for the study of spin-crossover systems based on metal clusters.

Original language	English
Pages (from-to)	21666-21677
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	115
Issue number	44
DOIs	https://doi.org/10.1021/jp207111r
State	Published - 10 Nov 2011

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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title = "Vibronic model for cooperative spin-crossover in pentanuclear {[M III(CN)6]2[MII(tmphen) 2]3} (M/M= Co/Fe, Fe/Fe) compounds",

abstract = "In this paper we present a microscopic model for the cooperative spin-crossover (SCO) phenomenon in crystals containing cyano-bridged pentanuclear clusters {[MIII(CN)6]2[M II(tmphen)2]3} (M/M= Co/Fe, 1; Fe/Fe, 2) with a trigonal bipyramidal (TBP) structure. The low-spin to high-spin (ls-hs) transition is considered as a cooperative phenomenon that is driven by the interaction of electronic shells of FeII ions with totally symmetric deformation of the local environment that is extended over the crystal lattice via the acoustic phonon field. Due to proximity of FeII ions in the cluster, the short-range intracluster interaction between these ions via the optical phonon field is included as well. The model takes into consideration also the spin-orbit coupling operating within the cubic 5T 2(t24e2) term of the hs-FeII ions. For cluster 2 the Heisenberg-type exchange interaction between the hs-Fe II and ls-FeIII ions is taken into account. The competition between short- and long-range interactions is shown to determine the type and temperature of the SCO transition in cluster systems. The proposed model explains, in a unique way, the temperature dependence of the static magnetic susceptibility and the M{\"o}ssbauer spectra of the title compounds. The approach described in this paper represents a theoretical tool for the study of spin-crossover systems based on metal clusters.",

author = "Sophia Klokishner and Serghei Ostrovsky and Andrei Palii and Michael Shatruk and Kristen Funck and Dunbar, {Kim R.} and Boris Tsukerblat",

year = "2011",

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AU - Klokishner, Sophia

AU - Ostrovsky, Serghei

AU - Palii, Andrei

AU - Shatruk, Michael

AU - Funck, Kristen

AU - Dunbar, Kim R.

AU - Tsukerblat, Boris

PY - 2011/11/10

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N2 - In this paper we present a microscopic model for the cooperative spin-crossover (SCO) phenomenon in crystals containing cyano-bridged pentanuclear clusters {[MIII(CN)6]2[M II(tmphen)2]3} (M/M= Co/Fe, 1; Fe/Fe, 2) with a trigonal bipyramidal (TBP) structure. The low-spin to high-spin (ls-hs) transition is considered as a cooperative phenomenon that is driven by the interaction of electronic shells of FeII ions with totally symmetric deformation of the local environment that is extended over the crystal lattice via the acoustic phonon field. Due to proximity of FeII ions in the cluster, the short-range intracluster interaction between these ions via the optical phonon field is included as well. The model takes into consideration also the spin-orbit coupling operating within the cubic 5T 2(t24e2) term of the hs-FeII ions. For cluster 2 the Heisenberg-type exchange interaction between the hs-Fe II and ls-FeIII ions is taken into account. The competition between short- and long-range interactions is shown to determine the type and temperature of the SCO transition in cluster systems. The proposed model explains, in a unique way, the temperature dependence of the static magnetic susceptibility and the Mössbauer spectra of the title compounds. The approach described in this paper represents a theoretical tool for the study of spin-crossover systems based on metal clusters.

AB - In this paper we present a microscopic model for the cooperative spin-crossover (SCO) phenomenon in crystals containing cyano-bridged pentanuclear clusters {[MIII(CN)6]2[M II(tmphen)2]3} (M/M= Co/Fe, 1; Fe/Fe, 2) with a trigonal bipyramidal (TBP) structure. The low-spin to high-spin (ls-hs) transition is considered as a cooperative phenomenon that is driven by the interaction of electronic shells of FeII ions with totally symmetric deformation of the local environment that is extended over the crystal lattice via the acoustic phonon field. Due to proximity of FeII ions in the cluster, the short-range intracluster interaction between these ions via the optical phonon field is included as well. The model takes into consideration also the spin-orbit coupling operating within the cubic 5T 2(t24e2) term of the hs-FeII ions. For cluster 2 the Heisenberg-type exchange interaction between the hs-Fe II and ls-FeIII ions is taken into account. The competition between short- and long-range interactions is shown to determine the type and temperature of the SCO transition in cluster systems. The proposed model explains, in a unique way, the temperature dependence of the static magnetic susceptibility and the Mössbauer spectra of the title compounds. The approach described in this paper represents a theoretical tool for the study of spin-crossover systems based on metal clusters.

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Vibronic model for cooperative spin-crossover in pentanuclear {[M ^III(CN)₆]₂[M^II(tmphen) ₂]₃} (M/M= Co/Fe, Fe/Fe) compounds

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