Correlations of the distribution of spin states in spin crossover compounds

Abstract

Short range correlations of the distribution of high spin (HS) and low spin (LS) states show up in thermal spin transition curves, decay curves of the light induced metastable HS state (LIESST state), and in structural features during the spin transitions. Correlations are due to short range interactions between the spin crossover molecules. Short range interactions may compete with omnipresent long range interactions and give rise to interesting spin transition phenomena. In this paper, the effect of correlations on the thermal spin transition in the mixed crystal system [Fe x Zn 1− x (pic) 3]Cl 2·EtOH (pic=picolylamine) is discussed. In particular the step in the thermal transition curve is a direct consequence of such correlations. In addition, the decay of the metastable HS state of the pure iron compound at ca. 20 K can be significantly changed by preparing metastable HS states with a random distribution over the lattice sites. Both experiments could be well reproduced by Monte Carlo simulations. In the orthorhombic modification of the compound Fe[5NO 2-sal-N(1,4,7,10)]([2,2′-(2,5,8,11-tetraazadodeca-1,11-diene-1,12-diyl)4-nitrophenolato] (2-)-N2, N2′,N2′′,N2′′′,O1, O1′]Fe(II)) a commensurable superstructure has been found. This compound represents the first example of a stable infinite range correlation of the spin states over the lattice sites.