Improved Visible Light Absorption of Potent Iridium(III) Photo-oxidants for Excited-State Electron Transfer Chemistry

Bevernaegie, Robin; Wehlin, Sara A. M.; Piechota, Eric J.; Abraham, Michael; Philouze, Christian; Meyer, Gerald J.; Elias, Benjamin; Troian-Gautier, Ludovic

doi:10.1021/jacs.9b12108

Title: Improved Visible Light Absorption of Potent Iridium(III) Photo-oxidants for Excited-State Electron Transfer Chemistry

Journal Article · 14 January 2020 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b12108 · OSTI ID:1801393

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UCLouvain, Louvain-la-Neuve (Belgium). Inst. de la Matière Condensée et des Nanosciences (IMCN). Molecular Chemistry, Materials and Catalysis (MOST); OSTI
Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
UCLouvain, Louvain-la-Neuve (Belgium). Inst. de la Matière Condensée et des Nanosciences (IMCN). Molecular Chemistry, Materials and Catalysis (MOST)
Univ. Grenoble-Alpes (UGA), Grenoble (France). Dept. de Chimie Moléculaire
Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Univ. Libre de Bruxelles (ULB), Brussels (Belgium). Lab. de Chimie Organique

Three iridium photosensitizers, [Ir(dCF₃ppy)₂(N–N)]⁺, where N–N is 1,4,5,8-tetraazaphenanthrene (TAP), pyrazino[2,3-a]phenazine (pzph), or benzo[a]pyrazino[2,3-h]phenazine (bpph) and dCF₃ppy is 2-(3,5-bis(trifluoromethyl-phenyl)pyridine), were found to be remarkably strong photo-oxidants with enhanced light absorption in the visible region. In particular, judicious ligand design provided access to Ir-bpph, with a molar absorption coefficient, ε = 9800 M^–1 cm^–1, at 450 nm and an excited-state reduction potential, E(Ir^+*/0) = 1.76 V vs NHE. These complexes were successful in performing light-driven charge separation and energy storage, where all complexes photo-oxidized seven different electron donors with rate constants (0.089-3.06) × 10¹⁰ M^–1 s^–1. A Marcus analysis provided a total reorganization energy of 0.7 ± 0.1 eV for excited-state electron transfer.

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Research Organization:: Univ. of North Carolina, Chapel Hill, NC (United States)

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

Grant/Contract Number:: SC0001011

OSTI ID:: 1801393

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Improved Visible Light Absorption of Potent Iridium(III) Photo-oxidants for Excited-State Electron Transfer Chemistry

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