Switching of Spin States Triggered by a Phase Transition:  Spin-Crossover Properties of Self-Assembled Iron(II) Complexes with Alkyl-Tethered Triazole Ligands

Iron(II) complexes of triazole derivatives having two C12 and C16 long alkyl chains, (C12trz)FeII and (C16trz)FeII, serve as novel spin-crossover materials, which display a spin-state transition in response to a phase transition. In contrast, a triazole complex with two C8 alkyl chains ((C8trz)FeII) exhibits only a poor response. EXAFS and XRD analyses of (C16trz)FeII indicate an interdigitating self-assembled structure of polynuclear iron(II) species. According to DSC, VT-IR, and VT-XRD profiles, the spin-state transition is triggered by melting of the interdigitating alkyl chains, which is likely responsible for the "lock-and-release" feature of the spin state. By virtue of the thermoreversibility of the phase transition, the spin crossover could be repeated without deterioration.