ic300750c_si_001.pdf (180.76 kB)
Theoretical Prediction of Spin-Crossover Temperatures in Ligand-Driven Light-Induced Spin Change Systems
journal contribution
posted on 2012-08-06, 00:00 authored by Jordi Cirera, Francesco PaesaniSpin-crossover compounds exhibit two alternative spin
states with
distinctive chemical and physical properties, a particular feature
that makes them promising materials for nanotechnological applications
as memory or display devices. A key parameter that characterizes these
compounds is the spin-crossover temperature, T1/2, defined as the temperature with equal populations of high
and low-spin species. In this study, a theoretical/computational approach
is described for the calculation of T1/2 for the trans-[Fe(styrylpyridine)4(NCX)2] (X = S, Se, and BH3, styrylpyridine in the trans configuration) ligand driven light-induced spin change
(LD-LISC) complexes. In all cases, the present calculations provide
an accurate description of both structural and electronic properties
of the LD-LISC complexes and, importantly, predict spin-crossover
temperatures in good agreement with the corresponding experimental
data. Fundamental insights into the dependence of T1/2 on the nature of the axial ligands are obtained from
the direct analysis of the underlying electronic structure in terms
of the relevant molecular orbitals.