Crystal-to-Crystal Synthesis of Photocatalytic Metal– Organic Frameworks for Visible-Light Reductive Coupling and Mechanistic Investigations

Abstract

Postmodification of reticular materials with well-defined cata- lysts is an appealing approach to produce new catalytic func- tional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal–organic frameworks (MOFs) to exploit the poten- tial of crystal-to-crystal transformations for further characteriza- tion of the catalysts. In this regard, two new photocatalytic materials, MOF-520-PC1 and MOF-520-PC2, are straightforward- ly obtained by the postfunctionalization of MOF-520 with pery- lene-3-carboxylic acid (PC1) and perylene-3-butyric acid (PC2). The single crystal-to-crystal transformation yielded the X-ray diffraction structure of catalytic MOF-520-PC2. The well-defined disposition of the perylenes inside the MOF served as suitable model systems to gain insights into the photophysical proper- ties and mechanism by combining steady-state, time-resolved, and transient absorption spectroscopy. The resulting materials are active organophotoredox catalysts in the reductive dimeri- zation of aromatic aldehydes, benzophenones, and imines under mild reaction conditions. Moreover, MOF-520-PC2 can be applied for synthesizing gram-scale quantities of products in continuous-flow conditions under steady-state light irradia- tion. This work provides an alternative approach for the con- struction of well-defined, metal-free, MOF-based catalysts.