Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction
KAUST DepartmentBiological and Environmental Sciences and Engineering (BESE) Division
Chemical Science Program
Homogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/561920
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AbstractDiels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
SponsorsJ. W. acknowledges financial support from Singapore DSTA DIRP Project (DSTA-NUS-DIRP/2008/03), the NRF Competitive Research Program (R-143-000-360-281), and A*Star BMRC grant (No. 10/1/21/19/642). K.-W. H. acknowledges financial support from KAUST.
JournalChemistry - A European Journal
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