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URN: urn:nbn:de:kobv:517-opus-11936
URL: http://opus.kobv.de/ubp/volltexte/2007/1193/


Dosche, Carsten ; Löhmannsröben, Hans-Gerd ; Bieser, A. ; Dosa, P. I. ; Han, S. ; Iwamoto, M. ; Schleifenbaum, A. ; Vollhardt, K. Peter C.

Photophysical properties of [N]phenylenes

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Kurzfassung in Englisch

In the present study, photophysical properties of [N]phenylenes were studied by means of stationary and time-resolved absorption and fluorescence spectroscopy (in THF at room temperature). For biphenylene (1) and linear [3]phenylene (2a), internal conversion (IC) with quantum yields ΦIC > 0.99 is by far the dominant mechanism of S1 state deactivation. Angular [3]phenylene (3a), the zig-zag [4]- and [5]phenylenes (3b), (3c), and the triangular [4]phenylene (4) show fluorescence emission with fluorescence quantum yieds and lifetimes between ΦF = 0.07 for (3a) and 0.21 for (3c) and τF = 20 ns for (3a) and 81 ns for (4). Also, compounds (3) and (4) exhibit triplet formation upon photoexcitation with quantum yields as high as ΦISC = 0.45 for (3c). The strong differences in the fluorescence properties and in the triplet fromation efficiencies between (1) and (2a) on one hand and (3) and (4) on the other are related to the remarkable variation of the internal conversion (IC) rate constants kIC. A tentative classification of (1) and (2a) as “fast IC compounds”, with kIC > 109 s-1, and of (3) and (4) as “slow IC compounds”, with kIC ≈ 107 s-1, is suggested. This classification cannot
simply be related to Hückel’s rule-type concepts of aromaticity, because the group of “fast IC compounds” consists of “antiaromatic” (1) and “aromatic” (2a), and the group of “slow IC compounds” consists of “antiaromatic” (3b), (4) and “aromatic” (3a), (3c). The IC in the [N]phenylenes is discussed within the framework of the so-called energy gap law established for non-radiative processes in benzenoid hydrocarbons.

Collection: Universität Potsdam / Aufsätze (Pre- und Postprints) / Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie / Physikalische Chemie
Institut: Institut für Chemie
DDC-Sachgruppe: Chemie
Dokumentart: c Postprint
Schriftenreihe: Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe, ISSN 1866-8372
Bandnummer: paper 001
Quelle: Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies. - ISSN 1463-9076. - 4 (2002), 11, p. 2156 - 2161
Sprache: Englisch
Erstellungsjahr: 2002
Publikationsdatum: 19.01.2007
Bemerkung:
first published in:
Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies. - ISSN 1463-9076. - 4 (2002), 11, S. 2156 - 2161
doi: 10.1039/b109342h
Reproduced by permission of the PCCP Owner Societies


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