title: Systematic investigation of photoinduced electron transfer controlled by internal charge transfer and its consequences for selective PdCl2 coordination.
abstract: Fluoroionophores of fluorophore-spacer-receptor format were prepared for detection of PdCl(2) by fluorescence enhancement. The fluorescent probes 1-13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl(2) 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 CH(2)-bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4-9 containing two anthracene or pyrene fragments connected through CH(2) bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (E(Ox)) through electron-withdrawing or -donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (DeltaG(PET)) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (Phi(f)), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl(2) were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10-13 were synthesized.
authors.affiliation: Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Golm, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Schwarze
authors.forename: Wulfhard
authors.initials: W
authors.lastname: Mickler
authors.forename: Carsten
authors.initials: C
authors.lastname: Dosche
authors.forename: Roman
authors.initials: R
authors.lastname: Flehr
authors.forename: Tillmann
authors.initials: T
authors.lastname: Klamroth
authors.forename: Hans-Gerd
authors.initials: HG
authors.lastname: Löhmannsröben
authors.forename: Peter
authors.initials: P
authors.lastname: Saalfrank
authors.forename: Hans-Jürgen
authors.initials: HJ
authors.lastname: Holdt
mesh_terms: D004563:Electrochemistry / Q000379:methods*; D004579:Electron Transport; D004583:Electrons / Q000009:adverse effects; D005456:Fluorescent Dyes / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction / Q000187:drug effects*; D010165:Palladium / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D055672:Static Electricity / Q000009:adverse effects; D013696:Temperature; D013816:Thermodynamics
chemical_list: D005456:Fluorescent Dyes; D010165:Palladium; C008756:palladium chloride