Engineering High-Potential Photo-oxidants with Panchromatic Absorption.

Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Jiang, T; Polizzi, NF; Rawson, J; Therien, MJ

Published Date

  • June 14, 2017

Published In

Volume / Issue

  • 139 / 25

Start / End Page

  • 8412 - 8415

PubMed ID

  • 28613070

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.7b04400

Language

  • eng