Redox state manipulation of a tris(p-tetrazolylphenyl)amine ligand and its Mn2+ coordination frameworks

Abstract

In situ spectroelectrochemical experiments coupled with UV/Vis/NIR, EPR, magnetism and fluorescence techniques have enabled insights into the electronic properties of the tris(p-tetrazolylphenyl)amine (H₃TTPA) ligand and the new Mn²⁺ frameworks [Mn₃(TTPA)₂(MeOH)₆]_n (1) and [Mn₃(TTPA)₂(DMF)₆]_n (2). Oxidation of H₃TTPA generated the triarylamine radical which was found to be delocalised throughout the ligand backbone. Solid state Vis/NIR and EPR spectroelectrochemical experiments on the frameworks were used to probe the optical properties of the accessible redox states and their relative stabilities, as well as the charge transfer interactions which were generated upon infiltration of electron acceptor guests. These studies provide a basis for the application of electroactive frameworks in functional electronic and optical devices, where knowledge of the properties of the distinct redox states and their interconversion is essential.