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Journal of Chemical Physics / Volume 103 / Issue 12

J. Chem. Phys. 103, 4894 (1995); http://dx.doi.org/10.1063/1.470625 (13 pages)

Vibronic coupling and energy transfer in bichromophoric molecules: The effect of symmetry

Niels A. van Dantzig1, Donald H. Levy1, Craig Vigo2, and Piotr Piotrowiak2

1Department of Chemistry and the James Franck Institute, University of Chicago, Chicago, Illinois 60637
2Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148

(Received 11 February 1994; accepted 22 June 1995)

The fluorescence spectra of a series of bichromophoric molecules consisting of covalently linked fluorene units were investigated in a supersonic jet. In three of the systems (spirobifluorene, d8h8‐spirobifluorene and 1‐methyl spirobifluorene) no electronic coupling and no corresponding exciton splitting were detected in the zero‐point level of the S1 state. Only 9,9′‐bifluorene exhibited an exciton splitting in the v=0 state. The lack of coupling was attributed to symmetry; in the spirobifluorenes the planes of the fluorene moieties and the S1←S0 transition moments are perpendicular. When low vibrational levels were excited, state mixing, and energy transfer between the chromophores was observed. This behavior is characteristic of the ‘‘small molecule’’ regime of radiationless transition theory. When higher vibrational levels were excited, the systems exhibited typical ‘‘large molecule’’ behavior. In this limit, both electronic energy transfer, as well as intramolecular vibrational relaxation contribute to the decay of the initially excited state. Intramolecular dispersive interactions were also investigated by comparing the bifluorenes with a series of reference compounds. © 1995 American Institute of Physics.

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KEYWORDS and PACS

Keywords

CHROMOPHORES, EXCITON−EXCITON INTERACTIONS, VIBRONIC STATES, ELECTRONIC STRUCTURE, ENERGY TRANSFER, FLUORENE, FLUORESCENCE SPECTROSCOPY, SYMMETRY, VIBRATIONAL STATES

PACS

  • 31.50.Df

    Potential energy surfaces for excited electronic states

  • 33.20.Wr

    Vibronic, rovibronic, and rotation-electron-spin interactions

  • 33.50.Dq

    Fluorescence and phosphorescence spectra

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.470625

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

For access to fully linked references, you need to log in.
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