A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis

Metal-organic frameworks (MOFs) have garnered substantial attention for their unique properties, such as high porosity and tunable structures, making them versatile for various applications. This paper constructs photoactive titanium-organic frameworks by combining Ti(IV) clusters and a bipyridine linker. The MOF is synthesized in situ through imine condensation, resulting in NU-2300. Subsequent ex situ nickel salt complexation results in NU-2300-Ni, which is then used for light-mediated carbon-heteroatom cross-couplings. The photophysical properties of the metallaphotocatalyst were investigated by UV-vis and EPR analyses, and both the Ti cluster and the bipyridine linker were found to contribute to successful catalysis, making it a tandem catalyst. The heterogeneous material retained its performance through five cycles of thioetherification. This work contributes not only to MOF synthetic strategies but also to expanding MOF applications as recyclable, tandem metallaphotocatalysts.