Photohalogen elimination chemistry in low-valent binuclear nickel complexes

The photogeneration of X2 is the key to achieving an efficient HX-splitting photocycle, as it more thermodynamically and kinetically challenging than its H2 half reaction counterpart. Here we report a strategy that enables Cl2 photoelimination from low-valent binuclear d9–d9 d9–d10 Ni complexes. We demonstrate importance metal–metal bond interaction for M–X photoactivation with combination TD-DFT computations together spectroscopy photocrystallography, exemplifying design principle future developments 3d metal complexes HX photocatalysis.