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Photoinduced Charge Separation in Cyclohexylidene‐Based Donor−(σ‐Bridge)−Acceptor Compounds − Building Blocks for Materials
Author(s) -
Oosterbaan Wibren D.,
van Gerven Paul C. M.,
van Walree Cornelis A.,
Koeberg Mattijs,
Piet Jacob J.,
Havenith Remco W. A.,
Zwikker Jan W.,
Jenneskens Leonardus W.,
Gleiter Rolf
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200200693
Subject(s) - chemistry , intramolecular force , photoexcitation , acceptor , photochemistry , absorption spectroscopy , aniline , spectroscopy , organic chemistry , physics , quantum mechanics , excited state , condensed matter physics , nuclear physics
We describe the syntheses and properties of five semi‐rigid donor−(σ‐bridge)−acceptor (D−σ−A) compounds. These compounds, which are candidates for incorporation in materials, have aniline‐type donors and (mixed) cyano‐ and alkoxycarbonyl‐1,1‐difunctionalized vinyl acceptors that are separated by a four‐σ‐bond bridge. Their electronic properties were studied by means of photoelectron spectroscopy in combination with ab initio MO calculations, cyclic voltammetry, UV‐Vis absorption spectroscopy, (time‐resolved) fluorescence spectroscopy, and time‐resolved microwave conductivity (TRMC). We found that these D−σ−A compounds exhibit a weak intramolecular charge‐transfer absorption band that borrows its intensity from local transitions. Upon photoexcitation, a charge‐separated state is generated in virtually quantitative yield. Conformational contraction or “folding” of this state takes place for the two D−σ−A compounds with a dicyanovinyl acceptor in apolar solvents. The absence of folding in compounds with an alkoxycarbonyl‐functionalized acceptor is attributed to a reduced lifetime of the charge‐separated state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)