Ultrafast Photophysics of Ni(I)–Bipyridine Halide Complexes: Spanning the Marcus Normal and Inverted Regimes

Owing to their light-harvesting properties, nickel–bipyridine (bpy) complexes have found wide use in metallaphotoredox cross-coupling reactions. Key to these transformations are Ni(I)–bpy halide intermediates that absorb a significant fraction of light at relevant cross-coupling reaction irradiation wavelengths. Herein, we report ultrafast transient absorption (TA) spectroscopy on a library of eight Ni(I)–bpy halide complexes, the first such characterization of any Ni(I) species. The TA data reveal the formation and decay of Ni(I)-to-bpy metal-to-ligand charge transfer (MLCT) excited states (10–30 ps) whose relaxation dynamics are well described by vibronic Marcus theory, spanning the normal and inverted regions as a result of simple changes to the bpy substituents. While these lifetimes are relatively long for MLCT excited states in first-row transition metal complexes, their duration precludes excited-state bimolecular reactivity in photoredox reactions. We also present a one-step method to generate an isolable, solid-state Ni(I)–bpy halide species, which decouples light-initiated reactivity from dark, thermal cycles in catalysis.