Mix and Match – Controlling the Functionality of Spin-Crossover Materials Through Solid Solutions and Molecular Alloys

The influence of dopant molecules on the structure and functionality of spin-crossover (SCO) materials is surveyed. Two aspects of the topic are well established. Firstly, isomorphous inert metal ion dopants in SCO lattices are a useful probe of the energetics of SCO processes. Secondly, molecular alloys of iron(II)/triazole coordination polymers containing mixtures of ligands were used to tune their spin-transitions towards room temperature. More recent examples of these and related materials are discussed that reveal new insights into these questions. Complexes which are not isomorphous can also be co-crystallised, either as solid solutions of the precursor molecules or as a random distribution of homo- and hetero-leptic centres in a molecular alloy. This could be a powerful method to manipulate SCO functionality. Published molecular alloys show different SCO behaviours, which may or may not include allosteric switching of their chemically distinct metal sites.