Polyhedron 2021, 203, 115228

The photogeneration of X2is the key to achieving an efficient HX-splitting photocycle, as it is more ther-modynamically and kinetically challenging than its H2half reaction counterpart. Here we report a strat-egy that enables Cl2photoelimination from low-valent binuclear d9–d9and d9–d10Ni complexes. Wedemonstrate the importance a of metal–metal bond interaction for M–X bond photoactivation with acombination of TD-DFT computations together with spectroscopy and photocrystallography, exemplify-ing a design principle for future developments of 3d metal complexes for HX photocatalysis


Seung Jun Hwang12, Ryan G. Hadt34, Serge Ruccoloa , David Gygi1 , Shao-LiangZheng1 , Yu-Sheng Chen5 , Daniel G. Nocera1

1 Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA

2 Department of Chemistry, POSTECH, Pohang 37673, South Korea

3 Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA

4 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA

5 ChemMatCARS, The University of Chicago, Argonne, IL 60439, USA