Shpol’skii spectroscopy and vibrational analysis of [N]phenylenes

  • Vibrationally resolved fluorescence spectra of four angular [N]phenylenes were recorded with laser excited Shpol’skii spectroscopy (LESS) in an n-octane matrix at 10 K. In general, the same vibrational frequencies were observed in the fluorescence excitation and emission spectra, indicating that the geometries of ground and electronically excited state are very similar. Because of intensity borrowing from the S2 state, vibrations of two different symmetries were observed in the fluorescence excitation spectra of angular [3]phenylene and zig-zag[5]phenylene. This finding allowed the location of the S2 state for these compounds. DFT calculations(RB3LYP/6-31G*) of the ground state vibrational frequencies were made. The calculated vibrational modes were in reasonably good agreement with the experimental data. A new very low-frequency vibration of approximately 100 cm-1 was predicted and experimentally confirmed for all [N]phenylenes investigated. This vibration seems to be unique for [N]phenylenes and is attributed to an in-plane movementVibrationally resolved fluorescence spectra of four angular [N]phenylenes were recorded with laser excited Shpol’skii spectroscopy (LESS) in an n-octane matrix at 10 K. In general, the same vibrational frequencies were observed in the fluorescence excitation and emission spectra, indicating that the geometries of ground and electronically excited state are very similar. Because of intensity borrowing from the S2 state, vibrations of two different symmetries were observed in the fluorescence excitation spectra of angular [3]phenylene and zig-zag[5]phenylene. This finding allowed the location of the S2 state for these compounds. DFT calculations(RB3LYP/6-31G*) of the ground state vibrational frequencies were made. The calculated vibrational modes were in reasonably good agreement with the experimental data. A new very low-frequency vibration of approximately 100 cm-1 was predicted and experimentally confirmed for all [N]phenylenes investigated. This vibration seems to be unique for [N]phenylenes and is attributed to an in-plane movement of the carbon backbone.show moreshow less

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Metadaten
Author:Carsten Dosche, Michael U. Kumke, F. Ariese, A. N. Bader, C. Gooijer, P. I. Dosa, S. Han, O. S. Miljanic, K. Peter C. Vollhardt, R. Puchta, N. J. R. van Eikema Hommes
URN:urn:nbn:de:kobv:517-opus-13075
Series (Serial Number):Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe (paper 024)
Document Type:Postprint
Language:German
Date of Publication (online):2007/04/13
Year of Completion:2003
Publishing Institution:Universität Potsdam
Release Date:2007/04/13
Source:Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies. - ISSN 1463-9076. - 5 (2003), p. 4563–4569
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Collections:Universität Potsdam / Aufsätze (Pre- und Postprints) / Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie / Physikalische Chemie
Notes extern:
first published in:
Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies. - ISSN 1463-9076. - 5 (2003), S. 4563–4569
doi: 10.1039/b308036f
Reproduced by permission of the PCCP Owner Societies