Facile redox state manipulation in Cu(i) frameworks by utilisation of the redox-active tris(4-(pyridin-4-yl)phenyl)amine ligand

Abstract

The incorporation of a redox-active tris(4-(pyridine-4-yl)phenyl)amine (NPy₃) ligand into the Cu(I) coordination frameworks [CuNPy₃NO₃·solvent]_n and [CuNPy₃Cl·solvent]_n has been shown to facilitate redox state switching in the materials. In both cases, the initial Cu(II) metal centre was reduced in situ during the solvothermal synthesis under relatively mild conditions where the use of chloride and nitrate counterions resulted in significantly different structures. Solid state electrochemical and Vis/NIR spectroelectrochemical experiments facilitated the characterisation and manipulation of the accessible redox states, demonstrating the highly tunable nature of the spectral properties – a property of significant interest in the design of advanced materials.