ABSTRACT
Two new fluorescent segmented conjugated polymers with either 1,4- or 2,6-distyrylnaphthalene chromophores and their model compounds were synthesized and the chemosensing abilities of the polymeric thin films to detect nitroaromatics (NACs) in aqueous media were evaluated. The structural, thermal and optical properties of the polymers were correlated with those displayed by their corresponding model compounds. Changes in the connectivity of naphthylene units caused minor differences in optical properties, morphology and quenching efficiencies. Molecular modeling highlighted the extremely bent character of polymer microstructures that explains their high solubility and amorphous character. Polymeric films are amorphous, strongly fluorescent and showed remarkable quenching efficiencies in the nanomolar range with picric acid (PA) and trinitrotoluene (TNT). Quenching experiments using either different nitroaromatic quenchers, excitation wavelengths, excitation beam path-lengths, or time of exposure of the film to the quenching solution evidenced the dominant role of inner filter effects (IFE) in the polymer response to NACs in the micromolar range. The sensing response towards PA, a quencher that strongly absorbs at the excitation wavelength, has an IFE contribution even at the nanomolar range, while the response towards the non-absorbing TNT depends only on the quenching occurring after diffusion of the analyte into the film.
ABSTRACT
The crystal structure of the dimeric title compound, C(19)H(22)O(5), is dominated by a head-to-head hydrogen-bonding interaction between centrosymmetrically related carboxyl groups in each monomer. The result is a dimeric axis of unusual length (ca 34 A), but still shorter than what could be expected for a fully extended chain, owing to two turning points in the oligoethoxy ends. This allows for an explanation of the structure of the smectic mesophase exhibited by this compound and at the same time fully validates former geometric estimations based on PM3 calculations.
