Supramolecular Control over Donor−Acceptor Photoinduced Charge Separation

A novel donor-bridge-acceptor system has been synthesized by covalently linking a p-phenylene vinylene oligomer (OPV) and a perylene diimid (PERY) at opposite ends of a m-phenylene ethynylene oligomer (FOLD) of twelve phenyl rings, containing nonpolar (S)-3,7-dimethyl-1-octanoxy side chains. For com...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-08, Vol.126 (31), p.9630-9644
Main Authors: Marcos Ramos, Alicia, Meskers, Stefan C. J, Beckers, Edwin H. A, Prince, Ryan B, Brunsveld, Luc, Janssen, René A. J
Format: Article
Language:English
Subjects:
Applied sciences
Electrical, magnetic and optical properties
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Properties and characterization
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Summary:A novel donor-bridge-acceptor system has been synthesized by covalently linking a p-phenylene vinylene oligomer (OPV) and a perylene diimid (PERY) at opposite ends of a m-phenylene ethynylene oligomer (FOLD) of twelve phenyl rings, containing nonpolar (S)-3,7-dimethyl-1-octanoxy side chains. For comparison, model compounds have been prepared in which either the donor or acceptor is absent. In chloroform, the oligomeric bridge is in a random coil conformation. Upon addition of an apolar solvent (heptane) the oligomeric bridge first folds into a helical stack and subsequently intermolecular self-assembly of the stacks into columnar architectures occurs. Photoexcitation in the random coil conformation, where the interaction between the donor and acceptor chromophores is small, results only in long-range intramolecular energy transfer in which the OPV singlet-excited state is transformed into the PERY singlet-excited state. In the folded conformation of the bridge, donor and acceptor are closer and their enhanced interaction favors the formation the OPV•+-FOLD-PERY•- charge-separated state upon photoexcitation. As a result, the extent of photoinduced charge separation depends on the degree of folding of the bridge between donor and acceptor and therefore on the apolar nature of the medium. As a consequence, and contrary to conventional photoinduced charge separation processes, the formation of the OPV•+-FOLD-PERY•- charge-separated state is more favored in apolar media.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0390909