Monitoring Chain Dynamics by Luminescence Using a Long-Lived Ruthenium Dye
-5-amino-1,10-phenanthroline hexafluorophosphate, RuNH2 , with a water
solubility of 1×10^?3 mol/L. 3,5-Dinitrobenzyl alcohol was found to be an efficient quencher
with a quenching rate constant of 2.7×10^9 M^?1 s^?1 as well as a water-solubility of 5×10^?3 mol/L. Both the dye and quencher were modified in a way such that they could be covalently linked to a polymer. RuNH2 was converted to bis-(2,2-bipyridine)-ruthenium(II)-5-isothiocyanato-1,10-
phenanthroline hexafluoro-phosphate, RuNCS, using thiophosgene to yield an active isothiocyanate group. 3,5-Dinitrobenzylamine, DNB-NH2 , was synthesized via tritylamination of the commercially available 3,5-dinitrobenzyl chloride.
A synthetic pathway has been established to covalently attach the dye and quencher to poly(N,N-dimethylacrylamide)(PDMA). Luminescence of this system was first characterized in N,N-dimethylformamide
(DMF) rather than water to allow for future comparisons to be made between this water-soluble system and the previously established non-water-soluble system. Luminescence analysis of the RuNCS labelled polymers in DMF could be fitted with a sum of three exponentials with the strongest contribution being that of a 1000 ns long-lived species which is characteristic of the free dye. A luminescence decay of a polymer labelled with both RuNCS and DNB-NH2 was acquired and showed static quenching of the ruthenium dye by the quencher.
School:University of Waterloo
School Location:Canada - Ontario
Source Type:Master's Thesis
Keywords:luminescence polymer dynamics ruthenium pdma chemistry
Date of Publication:01/01/2006