Abstract

We report the synthesis and characterization of self-assembled mono- and multilayers of {omega}-functionalized diacetylenic thiols. We used the carboxylic acid-terminated alkanethiol diacetylene HS(CH{sub 2}){sub 10}C=CC=VC(CH{sub 2}){sub 10}-COOH as a block for preparing multilayers. Individual layers are covalently bonded through a thioester linkage. These two orthogonal polymerization steps yield a highly structured three-dimensional, surface-confined polymer. The results of infrared external reflectance spectroscopy and ellipsometry clearly indicate layer-by-layer growth up to at the least 6 layers. The multilayers can be polymerized by UV irradiation either after the deposition of each individual layer or after all layers are deposited. The appearance of bands attributable to C=C vibrational modes in resonance Raman spectra confirms polymerization. Transmission UV-vis spectroscopy indicates the films consist of the highly conjugated blue polydiacetylenic polymer, and that polymerization is complete within 5 min of initial irradiation. 26 refs., 4 figs.

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