Through-Space Intervalence Charge Transfer as a Mechanism for Charge Delocalization in Metal-Organic Frameworks.

Understanding the nature of charge transfer mechanisms in 3-dimensional metal-organic frameworks (MOFs) is an important goal owing to the possibility of harnessing this knowledge to design electroactive and conductive frameworks. These materials have been proposed as the basis for the next generation of technological devices for applications in energy storage and conversion, including electrochromic devices, electrocatalysts, and battery materials. After nearly two decades of intense research into MOFs, the mechanisms of charge transfer remain relatively poorly understood, and new strategies to achieve charge mobility remain elusive and challenging to experimentally explore, validate, and model. We now demonstrate that aromatic stacking interactions in Zn(II) frameworks containing cofacial thiazolo[5,4- d]thiazole (TzTz) units lead to a mixed-valence state upon electrochemical or chemical reduction. This through-space intervalence charge transfer (IVCT) phenomenon represents a new mechanism for charge transfer in MOFs. Computational modeling of the optical data combined with application of Marcus-Hush theory to the IVCT bands for the mixed-valence framework has enabled quantification of the degree of charge transfer using both in situ and ex situ electro- and spectro-electrochemical methods. A distance dependence for the through-space electron transfer has also been identified on the basis of experimental studies and computational calculations. This work provides a new window into electron transfer phenomena in 3-dimensional coordination space, of relevance to electroactive MOFs where new mechanisms for charge transfer are highly sought after, and to understanding biological light-harvesting systems where through-space mixed-valence interactions are operative.