Controlling Spin Transition in One-Dimensional Coordination Polymers through Polymorphism

A series of polymer 1 microcrystals with several different morphologies have been systematically synthesized by controlling experimental parameters, namely concentration of reactants, temperature, solvent nature, and the use of surfactants, and their valence tautomerism (VT) has been studied by combined electron microscopy, X-ray diffraction data, and magnetization. Our results indicate that all of them can be grouped exclusively into two different crystalline phases, or a mixture of them, that critically determine the VT process, independent of the morphology and/or dimensions of the crystals. Moreover, a difference in the critical temperature of both phases by more than 50 K allows us to regulate VT. These results head the use of valence tautomeric ID polymers in devices where strict control and reproducibility of the switching behavior at different length scales and integration procedures is highly required.