Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction

Handle URI:
http://hdl.handle.net/10754/561920
Title:
Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction
Authors:
Li, Jinling; Jiao, Chongjun; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Wu, Jishan
Abstract:
Diels-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.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; KAUST Catalysis Center (KCC); Chemical Science Program; Physical Sciences and Engineering (PSE) Division; HCL
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
14-Nov-2011
DOI:
10.1002/chem.201102120
PubMed ID:
22083876
Type:
Article
ISSN:
09476539
Sponsors:
J. 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.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorLi, Jinlingen
dc.contributor.authorJiao, Chongjunen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorWu, Jishanen
dc.date.accessioned2015-08-03T09:34:08Zen
dc.date.available2015-08-03T09:34:08Zen
dc.date.issued2011-11-14en
dc.identifier.issn09476539en
dc.identifier.pmid22083876en
dc.identifier.doi10.1002/chem.201102120en
dc.identifier.urihttp://hdl.handle.net/10754/561920en
dc.description.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.en
dc.description.sponsorshipJ. 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.en
dc.publisherWiley-Blackwellen
dc.subjectcycloadditionen
dc.subjectdyes/pigmentsen
dc.subjecthyperconjugationen
dc.subjectMichael additionen
dc.subjectpolycyclesen
dc.titleLateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reactionen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentHCLen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singaporeen
kaust.authorHuang, Kuo-Weien
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