Two-Photon Study on the Electronic Interactions between the First Excited Singlet States in Carotenoid−Tetrapyrrole Dyads

Authors: Liao, P.-N., Pillai, S., Gust, D., Moore, T. A., Moore, A. L., and Walla, P. J.
Title: Two-Photon Study on the Electronic Interactions between the First Excited Singlet States in Carotenoid−Tetrapyrrole Dyads
Source: The Journal of Physical Chemistry A
Year: 2011
Volume: 115
Pages: 4082-4091

ABSTRACT:

Electronic interactions between the first excited states (S1) of carotenoids (Car) of different conjugation lengths (8−11 double bonds) and phthalocyanines (Pc) in different Car−Pc dyad molecules were investigated by two-photon spectroscopy and compared with Car S1−chlorophyll (Chl) interactions in photosynthetic light harvesting complexes (LHCs). The observation of Chl/Pc fluorescence after selective two-photon excitation of the Car S1 state allowed sensitive monitoring of the flow of energy between Car S1 and Pc or Chl. It is found that two-photon excitation excites to about 80% to 100% exclusively the carotenoid state Car S1 and that only a small fraction of direct tetrapyrrole two-photon excitation occurs. Amide-linked Car−Pc dyads in tetrahydrofuran demonstrate a molecular gear shift mechanism in that effective Car S1 → Pc energy transfer is observed in a dyad with 9 double bonds in the carotenoid, whereas in similar dyads with 11 double bonds in the carotenoid, the Pc fluorescence is strongly quenched by Pc → Car S1 energy transfer. In phenylamino-linked Car−Pc dyads in toluene extremely large electronic interactions between the Car S1 state and Pc were observed, particularly in the case of a dyad in which the carotenoid contained 10 double bonds. This observation together with previous findings in the same system provides strong evidence for excitonic Car S1−Pc Qy interactions. Very similar results were observed with photosynthetic LHC II complexes in the past, supporting an important role of such interactions in photosynthetic down-regulation.


Date of online publication: Tue, 2011-03-22
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