Theoretical Modeling of the Ligand-Tuning Effect over
the Transition Temperature in Four-Coordinated Fe<sup>II</sup> Molecules
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Abstract
Spin-crossover molecules are systems
of great interest due to their
behavior as molecular level switches, which makes them promising candidates
for nanoscale memory devices, among other applications. In this paper,
we report a computational study for the calculation of the transition
temperature (<i>T</i><sub>1/2</sub>), a key physical quantity
in the characterization of spin-crossover systems, for the family
of tetracoordinated Fe<sup>II</sup> transition-metal complexes of
generic formula [PhB(MesIm)<sub>3</sub>FeNPR<sub>1</sub>R<sub>2</sub>R<sub>3</sub>]. Our calculations correctly reproduce the experimentally
reported decrease in the <i>T</i><sub>1/2</sub> with an
increasing size of the phosphine and allow for the prediction of the <i>T</i><sub>1/2</sub> in new members of the family that are not
reported so far. More importantly, further insight into the factors
that control the fine-tuning of the <i>T</i><sub>1/2</sub> can be obtained by direct analysis of the underlying electronic
structure in terms of the relevant molecular orbitals
