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    Laser-Induced Fluorescence of Rhenocene in Low-Temperature Matrices: Selective Excitation and Emission


    Hill, Jeremy N. and Perutz, Robin N. and Rooney, A. Denise (1995) Laser-Induced Fluorescence of Rhenocene in Low-Temperature Matrices: Selective Excitation and Emission. Journal of Physical Chemistry A, 99. pp. 531-537. ISSN 1089-5639

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    Abstract

    Rhenocene, Re(?75-C5H5)2, has been generated by photolysis of Ref^-CsHs^H isolated in nitrogen and argon matrices at 12 K, and has been studied by laser-induced fluorescence with a pulsed tunable laser. The emission lifetime of the lowest LMCT excited state is (71.9 ± 1.3) ns in nitrogen and (69.3 ± 1.4) ns in argon matrices. The emission and excitation spectra are far simpler and much better resolved than the UV/vis absorption spectrum, because the laser selects individual sites/conformers in the matrix (or groups of sites with very similar absorptions). Vibrational progressions are detected which are based on the ring-metal-ring stretching mode, v4, and combinations of that mode with the symmetric ring breathing mode, v2, and the symmetric C—H deformation mode, v3. In the LMCT excited state, there is an increase in v4 of 5% and a decrease in v3 (9%) and v2 (3%), consistent with transfer of an electron from a ligand jr-orbital to a metal—ligand bonding orbital.

    Item Type: Article
    Additional Information: Cite as: J. Phys. Chem. 1995, 99, 2, 531–537
    Keywords: Laser-Induced; Fluorescence; Rhenocene; Low-Temperature; Matrices; Selective; Excitation; Emission;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 14522
    Identification Number: https://doi.org/10.1021/j100002a014
    Depositing User: Dr. Denise Rooney
    Date Deposited: 09 Jun 2021 14:31
    Journal or Publication Title: Journal of Physical Chemistry A
    Publisher: American Chemical Society
    Refereed: Yes
    URI:

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