Issue 24, 2013

Cooperative spin-crossover-like transitions in the inhomogeneous chain of exchange clusters

Abstract

A statistical theory of temperature-induced spin-crossover-like transitions has been developed for spin chains with a few exchange clusters in a unit cell. Using static magnetic susceptibility measurements, a general expression for the effective magnetic moment μeff of exchange clusters is obtained for an arbitrary structure of cluster terms. For heterospin Cu(hfac)2LR complexes (“breathing crystals”) with a “head-to-head” chain motif, a two-point approximation for a partition function of the Jahn–Teller Cu+2 paramagnetic center (spin 1/2) is suggested. Theoretical results are compared with available experimental data on thermal spin-crossover-like transitions in the “breathing crystal” compounds. It is shown that the model developed is able to successfully describe both of the cases of smooth and abrupt (cooperative) spin transitions for chains of three-spin exchange clusters. Spin-crossover-like transitions of a new type with step-wise changes in a positive exchange integral are predicted.

Graphical abstract: Cooperative spin-crossover-like transitions in the inhomogeneous chain of exchange clusters

Article information

Article type
Paper
Submitted
15 Feb 2013
Accepted
15 Apr 2013
First published
22 Apr 2013

Phys. Chem. Chem. Phys., 2013,15, 9931-9939

Cooperative spin-crossover-like transitions in the inhomogeneous chain of exchange clusters

V. A. Morozov, Phys. Chem. Chem. Phys., 2013, 15, 9931 DOI: 10.1039/C3CP50689D

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