Controlling Ground and Excited State Properties through Ligand Changes in Ruthenium Polypyridyl Complexes

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• 作者：Dennis L. Ashford ; Christopher R. K. Glasson ; Michael R. Norris ; Javier J. Concepcion ; Shahar Keinan ; M. Kyle Brennaman ; Joseph L. Templeton ; Thomas J. Meyer
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：June 2, 2014
• 年：2014
• 卷：53
• 期：11
• 页码：5637-5646
• 全文大小：544K
• 年卷期：v.53,no.11(June 2, 2014)
• ISSN：1520-510X

文摘

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鈥揘)]²⁺ (bpy = 2,2鈥?bipyridine; N鈥揘 is a bidentate polypyridyl ligand). In this series, the nature of the N鈥揘 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 蟺* orbitals on the N鈥揘 ligand results in more positive Ru^3+/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⁺ (位_max = 449 nm) with the lowest energy MLCT absorption appearing at 位_max = 564 nm. Emission energies decrease from 位_max = 650 nm to 885 nm across the series. One-mode Franck鈥揅ondon 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 Ru^3+/2+ potentials are assessed in the context of preparing low energy light absorbers for application in dye-sensitized photoelectrosynthesis cells.