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The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems

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Abstract

This manuscript discusses the photophysical behavior of transition metal complexes of Ru(II) and Os(II) employed in development of light harvesting arrays of chromophores. Particular emphasis is placed on the relationship between the photophysical behavior of complexes having metal-to-ligand charge transfer (MLCT) excited states and the electronic characteristics of bridging ligands used in preparing oligometallic complexes. Examples are presented that discuss intramolecular energy migration in complexes having two distinct MLCT chromophores with bridging ligands that only very weakly couple the two chromophores. In addition, systems having bridging ligands with localized triplet excited states lower in energy than the MLCT state of the metal center to which they are attached are discussed. These systems very often have excited states localized on the bridging ligand with excited state lifetimes on the order of tens of microseconds. Finally, systems having Fe(II) metal centers, with very low energy MLCT states, are discussed. In complexes also containing bridging ligands with low energy triplet states, energy partitioning between the Fe center MLCT state (or Fe localized ligand field states) and the ligand triplet state is observed; the two states relax to the ground state via parallel pathways, but the Fe(II) center does not serve as an absolute excitation energy sink.

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Acknowledgements

The authors wish to thank the U.S. Department of Energy, Division of Science (#DE-FG02–96 ER14617) for support of this work. In addition, RHS wishes to thank the many graduate and undergraduate students that contributed a great deal to this work; some of their efforts are recognized in the citations in this article.

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Authors and Affiliations

  1. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, 30332, USA

    Xian-yong Wang

  2. Laboratoire de Chimie Organique et Organométallique, Université Bordeaux I, CNRS UMR 5802, 33405, Talence cédex, France

    Andre Del Guerzo

  3. Scottish University, Kolkata, India

    Sujoy Baitalik

  4. Department of Chemistry, Frostburg State University, Frostburg, Maryland , 21532–2303, USA

    Gerald Simon

  5. Chemistry Division, Argonne National Laboratories, Argonne, IL, 60439, USA

    George B. Shaw & Lin X. Chen

  6. Department of Chemistry, Tulane University, New Orleans, LA, 70118, USA

    Russell Schmehl

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  1. Xian-yong Wang
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  2. Andre Del Guerzo
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  3. Sujoy Baitalik
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  4. Gerald Simon
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  6. Lin X. Chen
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  7. Russell Schmehl
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Correspondence to Russell Schmehl.

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Wang, Xy., Del Guerzo, A., Baitalik, S. et al. The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems. Photosynth Res 87, 83–103 (2006). https://doi.org/10.1007/s11120-005-9007-y

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  • DOI: https://doi.org/10.1007/s11120-005-9007-y

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