Excited State Bond Homolysis of Vanadium(V) Photocatalysts for Alkoxy Radical Generation

Barth, Alexandra T.; Pyrch, Austin J.; McCormick, Conor T.; Danilov, Evgeny O.; Castellano, Felix N.

doi:10.1021/acs.jpca.4c04250

Excited State Bond Homolysis of Vanadium(V) Photocatalysts for Alkoxy Radical Generation

Journal Article · Fri Aug 30 04:00:00 EDT 2024 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.4c04250· OSTI ID:2448533

^[1]; Pyrch, Austin J. ^[2]; McCormick, Conor T. ^[2]; ^[2]; ^[2]

North Carolina State University, Raleigh, NC (United States); North Carolina State University
North Carolina State University, Raleigh, NC (United States)

Advancements in photocatalysis have transformed synthetic organic chemistry, using light as a powerful tool to drive selective chemical transformations. Recent approaches have focused on metal-halide ligand-to-metal charge transfer (LMCT) photoactivated bond homolysis reactions leveraged by earth-abundant elements to generate valuable synthons for radical-mediated cross-coupling reactions. Of recent utility, oxovanadium(V) LMCT photocatalysts exhibit selective alkoxy radical generation from aliphatic alcohols upon blue light (UVA) irradiation under mild conditions. The selective photochemical liberation of alkoxy radicals is valuable for applying late-stage fragmentation approaches in organic synthesis and depolymerization strategies for nonbiodegradable polymers. Steady-state and time-resolved spectroscopy were used to assign the electronic structure of three well-defined V(V) photocatalysts in their ground and excited states. We assign the excited state for this transformation at earth-abundant vanadium(V), interrogating the electronic structure using static UV–visible absorption, ultrafast transient absorption, and electron paramagnetic resonance spectroscopy coupled to computational approaches. Furthermore, these findings afford assignments of the short-lived excited state intermediates that dictate selective homolytic bond cleavage in metal alkoxides, illustrating the valuable insight gleaned from fundamental investigations of the molecular photochemistry responsible for light-escalated chemical transformations.

View Accepted Manuscript (DOE)

Research Organization:: BioLEC EFRC, Princeton, NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019370

OSTI ID:: 2448533

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 36 Vol. 128; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption spectroscopy
absorption
bond homolysis
excited states
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photocatalysis
quantum mechanics
vanadium

Excited State Bond Homolysis of Vanadium(V) Photocatalysts for Alkoxy Radical Generation

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