Bodipy-Based Metal-Organic Frameworks Transformed in Solid States from 1D Chains to 2D Layer Structures as Efficient Visible Light Heterogeneous Photocatalysts for Forging C-B and C-C Bonds.

Boron dipyrromethene (also known as bodipy), as a class of versatile and robust fluorophores and a structural analogue of porphyrins, has received a great deal of interests in the field of light-harvesting and energy-transfer processes. However, the fabrication of bodipy monomers into metal-organic frameworks (MOFs) and the exploitation of their potential still lags behind the porphyrin MOFs. In this work, two bodipy-based MOFs, BMOF with 1D chain structure and BMOF with 2D layer structure, were assembled by using dicarboxyl-functionalized bodipy ligands. BMOF can also be converted to BMOF by inserting additional ligands into BMOF to cross-link the adjacent chains into the rhombic grid layer. During this process, spontaneous exfoliation occurred simultaneously and resulted in the formation of several hundred nanometer thickness BMOF (nBMOF ), which can be further exfoliated into one-layer MOF nanosheets (BMON ) by using the ultrasonic liquid exfoliation method in a high yield. Featuring the distinct bodipy scaffolds in the porous frameworks, both BMOF and BMON displayed high reactivity and recyclability in the photocatalytic inverse hydroboration and cross-dehydrogenative coupling reactions to afford α-amino organoborons and α-amino amides in moderate to high yields. This work not only highlights the cascade utilization of ligand installation and ultrasonic liquid exfoliation methods to provide the single-layer MOF sheets in high yields but also advances the bodipy-based MOFs as a new type of heterogeneous photocatalysts in the forging of C-B and C-C bonds driven by visible light.