Issue 30, 2015

Theoretical modeling of two-step spin-crossover transitions in FeII dinuclear systems

Abstract

A computational methodology to model the spin-transition in dinuclear iron(II) systems [Fe(bt)(NCX)2]2(μ-bpym) and [Fe(pypzH)(NCX)]2(μ-pypz)2 (X = S, Se or BH3) is presented. Using the hybrid meta-GGA exchange–correlation functional TPSSh, accurate values for the thermochemical quantities associated with the different spin-states can be computed, and subsequently used to calculate the corresponding transition temperatures. This result also allows for the correct modeling of the spin-crossover curve, in agreement with the two-step or single-step nature experimentally reported for the transition. Our results indicate that the presence or absence of a two-step transition is mostly dominated by electronic effects, and the cooperativity between binding pockets plays a minor role. Insight on the electronic structure effects that enhance or suppress this behavior and its origin can be outlined from direct analysis of the relevant d-based molecular orbitals, which allows for a quantitative computational prediction to screen for new dinuclear systems with selected properties.

Graphical abstract: Theoretical modeling of two-step spin-crossover transitions in FeII dinuclear systems

Supplementary files

Article information

Article type
Paper
Submitted
08 Mai 2015
Accepted
22 Jun 2015
First published
22 Jun 2015

J. Mater. Chem. C, 2015,3, 7954-7961

Theoretical modeling of two-step spin-crossover transitions in FeII dinuclear systems

J. Cirera and E. Ruiz, J. Mater. Chem. C, 2015, 3, 7954 DOI: 10.1039/C5TC01304F

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