Global compartmental analysis of the fluorescence decay surface of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)-trifluoro-methanesulfonate-end-capped poly(tetrahydrofuran
Hermans, Bart; De Schryver, Frans C; Van Stam, Janet al.
[en] The kinetic behavior of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]-ammonio)trifluoromethanesulfonate-end-capped poly(tetrahydrofuran) (POLYPROBE) in tetrahydrofuran is investigated by global compartmental analysis of the fluorescence decay surface. At low POLYPROBE concentrations the emission decays monoexponentially. When an analogous end-capped halato telechelic polymer without the pyrene chromophore ((N,N,N-triethylammonio)trifluoromethanesulfonate-end-capped poly(tetrahydrofuran), POLYSALT) is added to solutions containing a low POLYPROBE concentration, the emission can be fitted by a biexponential decay function. From these observations it is concluded that the second excited-state species in the POLYPROBE-POLYSALT system is POLYPROBE involved in ion aggregation due to dipole-dipole or ion-dipole interaction. At higher POLYPROBE concentrations, without added POLYSALT, a triexponential decay function is needed to describe the emission. The third excited-state species is POLYPROBE excimer, which can be formed via two pathways: either intermolecularly when a locally excited POLYPROBE encounters a ground-state POLYPROBE or intramolecularly when an aggregate of two POLYPROBE molecules rearranges. From the global compartmental analysis in which the value of one of the rate constants is scanned, it is found that the bimolecular processes are slowed down by the presence of the polymer chain, while intramolecular rearrangements are not affected.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Hermans, Bart; Katholieke Universiteit Leuven (KUL) > Department of Chemistry
De Schryver, Frans C; Katholieke Universiteit Leuven (KUL) > Department of Chemistry
Van Stam, Jan; Katholieke Universiteit Leuven (KUL) > Department of Chemistry
Boens, Noël; Katholieke Universiteit Leuven (KUL) > Department of Chemistry
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Trossaert, Geert; University of Ghent
Goethals, Eric; University of Ghent
Schacht, Etienne; University of Ghent
Language :
English
Title :
Global compartmental analysis of the fluorescence decay surface of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)-trifluoro-methanesulfonate-end-capped poly(tetrahydrofuran
Publication date :
24 April 1995
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
The Swedish Natural Science Research Council (NFR) through the European Human Capital and Mobility Scheme The "Belgian Fonds voor Geneeskundig Wetenschappelijk Onderzoek" (FGWO) BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
Funding text :
B.H. thanks the I.W.O.N.L. for a predoctoral fellowship. J.v.S. thanks the Swedish Natural Science Research Council (NFR) for a postdoctoral grant through the European Human Capital and Mobility Scheme. N.B. is an Onderzoeksleider of the Belgian Fonds voor Geneeskundig Wetenschappelijk Onderzoek (FGWO). Marcel Ameloot is thanked for
fruitful discussions. The financial support through IUAP-111-040a nd IUAP-11-16i s gratefully acknowledged.
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