Controlling ground and excited state properties through ligand changes in ruthenium polypyridyl complexes

Ashford, Dennis L., Glasson, Christopher R.K., Norris, Michael R., Concepcion, Javier J., Keinan, Shahar, Brennaman, M. Kyle, Templeton, Joseph L., and Meyer, Thomas J. (2014) Controlling ground and excited state properties through ligand changes in ruthenium polypyridyl complexes. Inorganic Chemistry, 53 (11). pp. 5637-5646.

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The capture and storage of solar energy requires chromophores that absorb light throughout the solar spectrum. We report here the synthesis, characterization, electrochemical, and photophysical properties of a series of Ru(II) polypyridyl complexes of the type [Ru(bpy)2(N–N)]2+ (bpy = 2,2'-bipyridine; N–N is a bidentate polypyridyl ligand). In this series, the nature of the N–N ligand was altered, either through increased conjugation or incorporation of noncoordinating heteroatoms, as a way to use ligand electronic properties to tune redox potentials, absorption spectra, emission spectra, and excited state energies and lifetimes. Electrochemical measurements show that lowering the π* orbitals on the N–N ligand results in more positive Ru3+/2+ redox potentials and more positive first ligand-based reduction potentials. The metal-to-ligand charge transfer absorptions of all of the new complexes are mostly red-shifted compared to Ru(bpy)32+ (λmax = 449 nm) with the lowest energy MLCT absorption appearing at λmax = 564 nm. Emission energies decrease from λmax = 650 nm to 885 nm across the series. One-mode Franck–Condon analysis of room-temperature emission spectra are used to calculate key excited state properties, including excited state redox potentials. The impacts of ligand changes on visible light absorption, excited state reduction potentials, and Ru3+/2+ potentials are assessed in the context of preparing low energy light absorbers for application in dye-sensitized photoelectrosynthesis cells.

Item ID: 33467
Item Type: Article (Research - C1)
ISSN: 1520-510X
Funders: US Department of Energy (DOE)
Projects and Grants: DOE Award DE-SC0001011, DOE Office of Science Graduate Fellowship Program, DOE Award DE-SC000129
Date Deposited: 17 Jun 2014 23:17
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 50%
03 CHEMICAL SCIENCES > 0305 Organic Chemistry > 030503 Organic Chemical Synthesis @ 50%
SEO Codes: 85 ENERGY > 8505 Renewable Energy > 850504 Solar-Photovoltaic Energy @ 50%
97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 50%
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