Paulo N. Martinho, Frederico F. Martins, Nuno A. G. Bandeira, and Maria José Calhorda

The capability of a given substance to change its spin state by the action of a stimulus, such as a change in temperature, is by itself a very challenging property. Its interest is increased by the potential applications and the need to find sustainable functional materials. 3D transition metal complexes, mainly with octahedral geometry, display this property when coordinated to particular sets of ligands. The prediction of this behavior has been attempted by many authors. It is, however, made very difficult because spin crossover (SCO), as it is called, occurs most often in the solid state, where besides complexes, counter ions, and solvents are also present in many cases. Intermolecular interactions definitely play a major role in SCO. In this review, we decided to analyze SCO in mono- and binuclear transition metal complexes containing halogens as ligands or as substituents of the ligands. The aim was to try and find trends in the properties which might be correlated to halogen substitution patterns. Besides a revision of the properties, we analyzed structures and other information. We also tried to build a simple model to run Density Functional Theory (DFT) calculations and calculate several parameters hoping to find correlations between calculated indices and SCO data. Although there are many experimental studies and single-crystal X-ray diffraction structures, there are only few examples with the F, Cl, Br and series. When their intermolecular interactions were not very different, T1/2 (temperature with 50% high spin and 50% low spin states) usually increased with the calculated ligand field parameter (Δoct) within a given family. A way to predict SCO remains elusive.

Doi: 10.3390/su12062512

Cited as: Martinho PN, Martins FF, Bandeira NAG, Calhorda MJ  (2020). Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies. Sustainability 12(6), 2512;