Crystallography and spin-crossover. A view of breathing materials

Abstract

The spin-crossover phenomenon (SCO) is a fascinating field that potentially concerns any material containing a (d⁴–d⁷) transition metal complex finding therefore an echo in as diverse research fields as chemistry, physics, biology and geology. Particularly, molecular and coordination-polymers SCO solids are thoroughly investigated since their bistability promises new routes towards a large panel of potential applications including smart pigments, optical switches or memory devices. Notwithstanding these motivating applicative targets, numerous fundamental aspects of SCO are still debated. Among them, the investigation of the structure–property relationships is unfailingly at the heart of the SCO research field. All the facets of the richness of the structural behaviors shown by SCO compounds are only revealed when exploring the whole sample scales – from atomic to macroscopic – all the external stimuli – temperature, pressure, light and any combinations and derived perturbations – and the various forms of the SCO compounds in the solid state – crystalline powders, single-crystals, poorly crystalline or nano-sized particles. Crystallography allows investigating all these aspects of SCO solids. In the past few years, crystallography has certainly been in a significant phase of development pushing the frontiers of investigations, in particular thanks to the progress in X-ray diffraction techniques. The encounter between SCO materials and crystallography is captivating, taking advantages from each other. In this paper, a personal account mainly based on our recent results provides perspectives and new approaches that should be developed in the investigation of SCO materials.