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Title: Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism

Artificial photosynthesis relies on coupling light absorption with chemical fuel generation. A mechanistic study of visible light-driven H 2 production from [Cp*Ir(bpy)H] + (1) has revealed a new, highly efficient pathway for integrating light absorption with bond formation. The net reaction of 1 with a proton source produces H 2, but the rate of excited state quenching is surprisingly acid-independent and displays no observable deuterium kinetic isotopic effect. Time-resolved photoluminescence and labeling studies are consistent with diffusion-limited bimetallic self-quenching by electron transfer. Accordingly, the quantum yield of H 2 release nearly reaches unity as the concentration of 1 increases. Furthermore, this unique pathway for photochemical H 2 generation provides insight into transformations catalyzed by 1.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0014255; SC0001011
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 41; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1351026
Alternate Identifier(s):
OSTI ID: 1425738

Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Brennaman, M. Kyle, and Miller, Alexander J. M.. Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism. United States: N. p., Web. doi:10.1021/jacs.6b08701.
Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Brennaman, M. Kyle, & Miller, Alexander J. M.. Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism. United States. doi:10.1021/jacs.6b08701.
Chambers, Matthew B., Kurtz, Daniel A., Pitman, Catherine L., Brennaman, M. Kyle, and Miller, Alexander J. M.. 2016. "Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism". United States. doi:10.1021/jacs.6b08701.
@article{osti_1351026,
title = {Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism},
author = {Chambers, Matthew B. and Kurtz, Daniel A. and Pitman, Catherine L. and Brennaman, M. Kyle and Miller, Alexander J. M.},
abstractNote = {Artificial photosynthesis relies on coupling light absorption with chemical fuel generation. A mechanistic study of visible light-driven H2 production from [Cp*Ir(bpy)H]+ (1) has revealed a new, highly efficient pathway for integrating light absorption with bond formation. The net reaction of 1 with a proton source produces H2, but the rate of excited state quenching is surprisingly acid-independent and displays no observable deuterium kinetic isotopic effect. Time-resolved photoluminescence and labeling studies are consistent with diffusion-limited bimetallic self-quenching by electron transfer. Accordingly, the quantum yield of H2 release nearly reaches unity as the concentration of 1 increases. Furthermore, this unique pathway for photochemical H2 generation provides insight into transformations catalyzed by 1.},
doi = {10.1021/jacs.6b08701},
journal = {Journal of the American Chemical Society},
number = 41,
volume = 138,
place = {United States},
year = {2016},
month = {9}
}