Catalytic Hydrosilylation Routes to Divinylbenzene Bridged Silole and Silafluorene Polymers. Applications to Surface Imaging of Explosive Particulates

Catalytic Hydrosilylation Routes to Divinylbenzene Bridged Silole and Silafluorene Polymers. Applications to Surface Imaging of Explosive Particulates

The syntheses, spectroscopic characterization, and fluorescence quenching efficiencies of 1,1-silole− and 1,1-silafluorene−phenylenedivinylene polymers are reported. Model dimeric metallole compounds containing a phenylenedivinylene bridge have been synthesized to provide detailed structural and spe...

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Bibliographic Details
Published in:Macromolecules Vol. 41; no. 4; pp. 1237 - 1245
Main Authors: Sanchez, Jason C, Urbas, Sara A, Toal, Sarah J, DiPasquale, Antonio G, Rheingold, Arnold L, Trogler, William C
Format: Journal Article
Language:English
Published: Washington, DC American Chemical Society 26-02-2008
Subjects:
Applied sciences
Exact sciences and technology
Inorganic and organomineral polymers
Physicochemistry of polymers
Preparation
Nitro compound
Silane copolymer
Silicon heterocycle
Heterocyclic copolymer
Fluorescence
Stereospecific polymer
Hydrosilylation
Chemical sensor
Experimental study
Polyaddition
Cardo polymer
Conjugated copolymer
Optical properties
Preparation
Trans stereoisomer
Luminescence quenching
Detection threshold
Explosives
Diynic compound
Phenylenevinylene copolymer
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Summary:The syntheses, spectroscopic characterization, and fluorescence quenching efficiencies of 1,1-silole− and 1,1-silafluorene−phenylenedivinylene polymers are reported. Model dimeric metallole compounds containing a phenylenedivinylene bridge have been synthesized to provide detailed structural and spectroscopic insight into conformational effects and electron delocalization. Poly((tetraphenyl)silole−phenylenedivinylene) and poly(silafluorene−phenylenedivinylene) both maintain a regioregular trans-vinylene Si−C backbone with σ*−π/π* conjugation. Various hydrosilylation catalysts were screened to evaluate their ability to produce high molecular weight polymers and to direct a strictly trans product. Molecular weights (M w) for these polymers are in the range of 8400−9600. Fluorescence spectroscopy shows a significant bathochromic shift for the silafluorene polymer from solution to the solid state. A surface detection method for the analysis of solid particulates of TNT, DNT, PA, RDX, HMX, Tetryl, TNG, and PETN by fluorescence quenching was explored. The blue-emitting silafluorene polymer exhibited improved sensitivity for detecting explosive particle residues as compared to previously reported metallole polymers. Detection limits as low as 100 pg cm-2 for TNT are obtained. The Stern−Volmer equation quantitatively models the fluorescence quenching of these polymers by TNT, RDX, and PETN in thin solid-state films.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma702274c