Donor‐Functionalized Polydentate Pyrylium Salts and Phosphinines: Synthesis, Structural Characterization, and Photophysical Properties
2007; Wiley; Volume: 13; Issue: 16 Linguagem: Inglês
10.1002/chem.200601650
ISSN1521-3765
AutoresChristian Müller, Dorothee Wasserberg, Jarno J. M. Weemers, Evgeny A. Pidko, S.M.A. Hoffmann, Martin Lutz, Anthony L. Spek, Stefan C. J. Meskers, René A. J. Janssen, Rutger A. van Santen, Dieter Vogt,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoAbstract A series of donor‐functionalized pyrylium salts have been prepared by classical condensation reactions which were further converted into the corresponding thienyl‐ and pyridyl‐substituted polydentate λ 3 ‐phosphinines by reaction with P(SiMe 3 ) 3 . Further chemical modification of these phosphorus heterocycles with Hg(OAc) 2 in the presence of methanol resulted in the formation of λ 5 ‐phosphinines. The photophysical properties of a selected series of thienyl‐ and pyridyl‐functionalized pyrylium salts, λ 3 ‐ and λ 5 ‐phosphinines, were investigated and the results compared and supported by theoretical calculations on the DFT level. Significant fluorescence was observed for the pyrylium salts and λ 5 ‐phosphinines. In contrast, the heteroaromatic substituted λ 3 ‐phosphinines show very little emission which is consistent with the low oscillator strength predicted by DFT calculations for this π→π* transition. Furthermore, all three classes of compounds show readily observable phosphorescence in solution, which was determined by time‐gated detection at low temperature.
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