Publications [#327332] of Michael J. Therien

Papers Published

1. Jiang, T; Polizzi, NF; Rawson, J; Therien, MJ, Engineering High-Potential Photo-oxidants with Panchromatic Absorption., Journal of the American Chemical Society, vol. 139 no. 25 (June, 2017), pp. 8412-8415 [doi]
   (last updated on 2024/04/25)

   Abstract:
   Challenging photochemistry demands high-potential visible-light-absorbing photo-oxidants. We report (i) a highly electron-deficient Ru(II) complex (eDef-Rutpy) bearing an E_1/2^0/+ 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 E_1/2^0/+ potential, comparable to that of Ce(NH₄)₂(NO₃)₆ [E_1/2(Ce^3+/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.