Pore Engineering in Triptycene-Based Copper Metal–Organic Frameworks for High-Efficiency Photocatalytic Hydroboration

The photocatalytic performance of metal–organic frameworks (MOFs) depends on the synergistic regulation of metal node, organic ligand, and topological structure, yet improving the recyclability and scalability of heterogeneous catalysts remains a significant challenge. Herein, we demonstrate that metal precursor selection critically controls both framework topology and catalytic activity in copper-based MOFs. Using a newly designed hexapyridyl triptycene ligand and deliberately varying copper salts (CuCN vs CuCl 2 ), two topologically distinct MOFs, XJUM-1 and XJUM-2, with different pore size and photochemical properties were constructed. XJUM-2 exhibits a unique 6,4-connected 2-fold interpenetrated structure-unprecedented in cyanide-bridged systems-achieved through precise modulation of cyanide-bridge density. This structural control directly enhances charge separation, pore regularity, and catalytic performance. As a result, XJUM-2 delivers record-breaking activity for photocatalytic hydroboration of styrene (TOF = 86.4 h –1, the highest among Cu-MOFs), alongside exclusive anti-Markovnikov selectivity, broad substrate scope (40 examples), and robust recyclability (>92% yield over 5 cycles). Our work transcends conventional ligand/metal-node engineering, demonstrating that metal precursor choice is a critical, previously overlooked handle for programming MOF topology and reactivity in organic transformations.