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Mono- and dinuclear ruthenium(II) and osmium(II) polypyridine complexes built around spiro-bridged bis(phenanthroline) ligands: Synthesis, electrochemistry, and photophysics

Lookup NU author(s): Emeritus Professor Anthony Harriman

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Abstract

Two new dyads have been synthesized in which terminal Ru(II) and Os(II) polypyridine complexes are separated by sterically constrained spiro bridges. The photophysical properties of the corresponding mononuclear complexes indicate the importance of the decay of the lowest-energy triplet states localized on the metallo fragments through the higher-energy metal-centered excited states. This effect is minimized at 77 K, where triplet lifetimes are relatively long, and for the Os(II)-based systems relative to their Ru(II)-based counterparts. Intramolecular triplet energy transfer takes place from the Ru(II)-based fragment to the appended Os(II)-based unit, the rate constant being dependent on the molecular structure and on temperature. In all cases, the experimental rate constant matches surprisingly well with the rate constant calculated for Forster-type dipole - dipole energy transfer. As such, the disparate rates shown by the two compounds can be attributed to stereochemical factors. It is further concluded that the spiro bridging unit does not favor through-bond electron exchange interactions, a situation confirmed by cyclic voltammetry.

Publication metadata

Author(s): Juris A, Prodi L, Harriman A, Ziessel R, Hissler M, El-ghayoury A, Wu F, Riesgo EC, Thummel RP

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2000

Volume: 39

Issue: 16

Pages: 3590-3598

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic0000202

DOI: 10.1021/ic0000202

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