Relationship between the Molecular Structure and Switching Temperature in a Library of Spin-Crossover Molecular Materials.

Structure-function relationships relating the spin-crossover (SCO) midpoint temperature () in the solid state are surveyed for 43 members of the iron(II) dipyrazolylpyridine family of SCO compounds. The difference between in the solid state and in solution [Δ(latt)] is proposed as a measure of the lattice contribution to the transition temperature. Negative linear correlations between the SCO temperature and the magnitude of the rearrangement of the coordination sphere during SCO are evident among isostructural or near-isostructural subsets of compounds; that is, a larger change in the molecular structure during SCO stabilizes the high-spin state of a material. Improved correlations are often obtained when Δ(latt), rather than the raw value, is considered as the measure of the SCO temperature. Different lattice types show different tendencies to stabilize the high-spin or low-spin state of the molecules they contain, which correlates with the structural changes that most influence Δ(latt) in each case. These relationships are mostly unaffected by the SCO cooperativity in the compounds or by the involvement of any crystallographic phase changes. One or two materials within each subset are outliers in some or all of these correlations, however, which, in some cases, can be attributed to small differences in their ligand geometry or unusual phase behavior during SCO. A reinvestigation of the structural chemistry of [Fe(3-bpp)][NCS]·HO [3-bpp = bis(1-pyrazol-3-yl)pyridine; = 0 or 2], undertaken as part of this study, is also presented.