Halogenated Alkyltetrazoles for the Rational Design of Fe Spin-Crossover Materials: Fine-Tuning of the Ligand Size.

1-(3-Halopropyl)-1H-tetrazoles and their corresponding Fe spin-crossover complexes have been investigated in a combined experimental and theoretical study. Halogen substitution was found to positively influence the spin transition, shifting the transition temperature about 70 K towards room temperature. Halogens located at the ω position were found to be too far away from the coordinating tetrazole moiety to have an electronic impact on the spin transition. The subtle variation of the steric demand of the ligand in a highly comparable series was found to have a comparatively large impact on the spin-transition behavior, which highlights the sensitivity of the effect to subtle structural changes.