5 years ago

Engineering High-Potential Photo-oxidants with Panchromatic Absorption

Engineering High-Potential Photo-oxidants with Panchromatic Absorption
Jeff Rawson, Nicholas F. Polizzi, Michael J. Therien, Ting Jiang
Challenging photochemistry demands high-potential visible-light-absorbing photo-oxidants. We report (i) a highly electron-deficient Ru(II) complex (eDef-Rutpy) bearing an E1/20/+ potential more than 300 mV more positive than that of any established Ru(II) bis(terpyridyl) derivative, and (ii) an ethyne-bridged eDef-Rutpy−(porphinato)Zn(II) (eDef-RuPZn) supermolecule that affords both panchromatic UV–vis spectral domain absorptivity and a high E1/20/+ potential, comparable to that of Ce(NH4)2(NO3)6 [E1/2(Ce3+/4+) = 1.61 V vs NHE], a strong and versatile ground-state oxidant commonly used in organic functional group transformations. eDef-RuPZn exhibits ∼8-fold greater absorptive oscillator strength over the 380–700 nm range relative to conventional Ru(II) polypyridyl complexes, and impressive excited-state reduction potentials (1E–/* = 1.59 V; 3E–/* = 1.26 V). eDef-RuPZn manifests electronically excited singlet and triplet charge-transfer state lifetimes more than 2 orders of magnitude longer than those typical of conventional Ru(II) bis(terpyridyl) chromophores, suggesting new opportunities in light-driven oxidation reactions for energy conversion and photocatalysis.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b04400

DOI: 10.1021/jacs.7b04400

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