• search hit 6 of 6
Back to Result List

Systematic investigation of photoinduced electron transfer controlled by internal charge transfer and its consequences for selective PdCl2 coordination

  • Fluoroionophores of fluorophore-spacer-receptor format were prepared for detection of PdCl2 by fluorescence enhancement. The fluorescent probes 1-13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl2 receptor. First, varying the length of the alkylene spacer (compounds 1-3) revealed a dominant through-space pathway for oxidative photoinduced electron transfer (PET) in CH2-bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4-9 containing two anthracene or pyrene fragments connected through CH2 bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (EOx) through electron-withdrawing or -donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (GPET) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (f), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl2 were achieved by 7 andFluoroionophores of fluorophore-spacer-receptor format were prepared for detection of PdCl2 by fluorescence enhancement. The fluorescent probes 1-13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl2 receptor. First, varying the length of the alkylene spacer (compounds 1-3) revealed a dominant through-space pathway for oxidative photoinduced electron transfer (PET) in CH2-bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4-9 containing two anthracene or pyrene fragments connected through CH2 bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (EOx) through electron-withdrawing or -donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (GPET) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (f), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl2 were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10-13 were synthesized.show moreshow less

Export metadata

Additional Services

Share in Twitter Search Google Scholar Statistics
Metadaten
Author:Thomas Schwarze, Wulfhard Mickler, Carsten DoscheGND, Roman FlehrGND, Tillmann Klamroth, Hans-Gerd LöhmannsröbenGND, Peter SaalfrankORCiDGND, Hans-Jürgen Holdt
URL:http://www3.interscience.wiley.com/journal/26293/home
ISSN:0947-6539
Document Type:Article
Language:English
Year of first Publication:2010
Year of Completion:2010
Release Date:2017/03/25
Source:Chemistry : a European journal. - ISSN 0947-6539. - 16 (2010), 6, S. 1819 - 1825
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert