Lewis acid–base interactions enhance explosives sensing in silacycle polymers

Abstract

The high sensitivity of silole- and silafluorene-containing polymers for detecting organic nitro, nitrate, and nitramine explosives cannot be solely attributed to favorable analyte–polymer hydrophobic interactions and amplified fluorescence quenching due to delocalization along the polymer chain. The Lewis acidity of silicon in conjugated poly(silafluorene-vinylene)s is shown to be important. This was established by examining the ²⁹Si NMR chemical shifts (Δ) for the model trimer fragment of the polymer CH ₃–silafluorene–( trans-C ₂H ₂)–silafluorene–( trans-C ₂H ₂)–silafluorene–CH ₃. The peripheral and central silicon resonances are up-field from a TMS reference at −9.50 and −18.9 ppm, respectively. Both resonances shift down-field in the presence of donor analytes and the observed shifts (0 to 1 ppm) correlate with the basicity of a variety of added Lewis bases, including TNT. The most basic analyte studied was acetonitrile and an association constant ( K _a) of 0.12 M ⁻¹ was calculated its binding to the peripheral silicon centers using the Scatchard method. Spin-lattice relaxation times ( T ₁) of 5.86(3) and 4.83(4) s were measured for the methyl protons of acetonitrile in benzene- d ₆ at 20 °C in the absence and presence of the silafluorene trimer, respectively. The significant change in T ₁ values further supports a binding event between acetonitrile and the silafluorene trimer. These studies as well as significant changes and shifts observed in the characteristic UV–Vis absorption of the silafluorene group support an important role for the Lewis acid character of Si in polymer sensors that incorporate strained silacycles. The nitro groups of high explosives may act as weak Lewis-base donors to silacycles. This provides a donor–acceptor interaction that may be crucial for orienting the explosive analyte in the polymer film to provide an efficient pathway for inner-sphere electron transfer during the electron-transfer quenching process.

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Electronic supplementary material

The online version of this article (doi:10.1007/s00216-009-2846-1) contains supplementary material, which is available to authorized users.