Recent advances in chromium(III) photocatalysis have demonstrated the potential of earth-abundant reagents to promote organic transformations where reaction pathways are different from those observed in Ru-initiated systems. These Cr polypyridyl species exhibit extremely long excited state lifetimes while most other first-row metal complexes display much shorter lifetimes. To better understand the photophysics and photochemistry of these Cr(III) systems, we have synthesized and characterized isoelectronic vanadium(II) analogues. Ultrafast time-resolved spectroscopy shows a short-lived excited state before interconversion to the long-lived (τ &gt; 400 ps) component reported by Shah and Maverick. We have investigated various metal- and ligand-based electronic states and assigned their relative energies using several spectroscopic and computational techniques. These studies suggest that the low energy <sup>2</sup>E in V(II) polypyridyl complexes decay to the ground state more rapidly when compared to their Cr(III) analogues. We have applied these results towards the design of (ligand) localized charge in photocatalytic systems. Complex preparations, electronic transitions, (spectro)electrochemistry and electronic structure calculations will be presented.<br/>

Comparison of the photophysical and photochemical properties of vanadium and chromium polypyridyl complexes

254th National Meeting (2017)

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