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Issue 29, 2011
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Phenomenological model of spin crossover in molecular crystals as derived from atom–atom potentials

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Abstract

The method of atom–atom potentials, previously applied to the analysis of pure molecular crystals formed by either low-spin (LS) or high-spin (HS) forms (spin isomers) of Fe(II) coordination compounds (Sinitskiy et al., Phys. Chem. Chem. Phys., 2009, 11, 10983), is used to estimate the lattice enthalpies of mixed crystals containing different fractions of the spin isomers. The crystals under study were formed by LS and HS isomers of Fe(phen)2(NCS)2 (phen = 1,10-phenanthroline), Fe(btz)2(NCS)2 (btz = 5,5′,6,6′-tetrahydro-4H,4′H-2,2′-bi-1,3-thiazine), and Fe(bpz)2(bipy) (bpz = dihydrobis(1-pyrazolil)borate, and bipy = 2,2′-bipyridine). For the first time the phenomenological parameters Γ pertinent to the Slichter–Drickamer model (SDM) of several materials were independently derived from the microscopic model of the crystals with use of atom–atom potentials of intermolecular interaction. The accuracy of the SDM was checked against the numerical data on the enthalpies of mixed crystals. Fair semiquantitative agreement with the experimental dependence of the HS fraction on temperature was achieved with use of these values. Prediction of trends in Γ values as a function of chemical composition and geometry of the crystals is possible with the proposed approach, which opens a way to rational design of spin crossover materials with desired properties.

Graphical abstract: Phenomenological model of spin crossover in molecular crystals as derived from atom–atom potentials

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Publication details

The article was received on 20 Feb 2011, accepted on 25 May 2011 and first published on 23 Jun 2011


Article type: Paper
DOI: 10.1039/C1CP20440H
Citation: Phys. Chem. Chem. Phys., 2011,13, 13238-13246
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    Phenomenological model of spin crossover in molecular crystals as derived from atom–atom potentials

    A. V. Sinitskiy, A. L. Tchougréeff and R. Dronskowski, Phys. Chem. Chem. Phys., 2011, 13, 13238
    DOI: 10.1039/C1CP20440H

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