Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal–organic framework via single crystal electronic absorption spectroscopy†
Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal–Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure–property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(II)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole, tdc2− = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus–Hush theory. The electronic coupling constant, Hab, of 145 cm−1 was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alternative methods to obtain the Hab parameter. This work demonstrates the first report of the successful characterisation of IVCT in a MOF material using single crystal electronic absorption spectroscopy and serves as an attractive alternative to more complex methods due to its simplicity and applicability.