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Photoswitches Containing a Dithiafulvene Electron Donor
Author(s) -
Åxman Petersen M.,
Zhu L.,
Jensen S. H.,
Andersson A. S.,
Kadziola A.,
Kilså K.,
Brøndsted Nielsen M.
Publication year - 2007
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200600888
Subject(s) - isomerization , chromophore , photochemistry , conjugated system , materials science , fluorescence , absorption (acoustics) , ring (chemistry) , spectroscopy , absorption spectroscopy , chemistry , optics , physics , organic chemistry , catalysis , quantum mechanics , polymer , composite material
Three new chromophores containing an electron‐donating dithiafulvene (DTF) unit attached to derivatives of retinal, diethynylethene (DEE), and dihydroazulene (DHA), respectively, are synthesized and characterized by using X‐ray crystallography as well as absorption and fluorescence spectroscopy. In general, the DTF unit induces a significant red‐shift in the lowest‐energy absorption in all investigated chromophores. The influence of the DTF unit on light‐induced cis–trans isomerization and on retro‐electrocyclization is investigated. Although the retinylidene derivative decomposes when subjected to light, the DTF‐functionalized DEE and DHA compounds undergo reversible isomerization. Computations show that the highest occupied molecular orbital (HOMO) of DTF–DHA is spread over most of the π‐conjugated system, whereas it is more localized in the ring‐opened product. This difference is reflected in the redox properties.