A symmetrical 2-thiopyrimidine based molecule with an expanded p-electron system is synthesized and used to form a self-assembled monolayer (SAM) on gold surfaces. Utilizing chemical vapor deposition a monolayer of (3-mercaptopropyl)triethoxysilane is formed on silicon dioxide substrates. Both of these SAM coated substrates are characterized by Xray photoelectron spectroscopy and the growth of a coordination polymer built up from 5,5 0 -(ethyne-1,2-diyl)bis(2-hydroxyacetophenone) and copper(II) on dual SAM coated transducers is studied. After the deposition procedure on interdigital elec-trodes the electrical properties of the polymer are investigated performing resistive measurements. A significant change of the resistance, which depends on the surrounding atmosphere, proves the sensing behavior of the synthesized coordination polymer.
Two new linker-type molecules 1a and 1b composed of o-hydroxyacetophenone coordinative groups attached to linear ethynylene or 1,4-phenylenediethynylene spacer units have been synthesised and structurally characterised. An X-ray crystallographic study for both compounds has shown structures with strong intramolecular hydrogen bonds fitting in the model of 'Intramolecular Resonance Assisted Hydrogen Bond (IRHAB)'. Initial coordination experiments with Cu(II) were performed and the resulting materials characterised by PXRD. The similarity of the copper coordination between these compounds and copper(II) acetylacetonate complexes was demonstrated by XPS measurements. Based on the evidence of these studies, and on elemental analysis, the formation of the corresponding coordination polymers comprising Cu(II) and the linkers has been proposed.
Chemiresistive composites of gold (Au) nanoparticles interlinked with different types of organic molecules were prepared automatically by layer-by-layer self-assembly using a microfluidic cell. For the assembly process, dodecylamine-stabilized Au nanoparticles with an average size of 3.7 nm as well as alkyl dithiols, alkyl diamines, and alkyl bisdithiocarbamates with different alkyl chain length (C6 and C8) were used. X-ray photoelectron spectroscopy was applied on prepared nanoparticle composites to study the film composition and the degree of interlinkage. For the measurement of electrical and vapor-sensing properties, silicon dies equipped with gold interdigitated electrodes were used. All films show linear current-voltage characteristics and conductivities in the range of 10–2 and 10–4 Ω−1 cm−1 at room temperature. The sensitivity of the film is investigated by dosing them with vapors of toluene, 1-propanol, 4-methyl-2-pentanone, and water in the concentration range from 100 to 5,000 ppm at 0% relative humidity. All composite films respond with an increase in their electrical resistance to the analytes. The sensors show a high signal-to-noise ratio which indicates a detection limit below 100 ppm for all test vapors. The response dynamics demonstrate a high reversibility and a fast sensing mechanism especially for dithiols and diamines with response and recovery times from 2 to 10 s. The dithiol sensors exhibit a high selectivity to toluene and 4-methyl-2-pentanone whereas the bisdithiocarbamate composites are suitable for the detection of water and 1-propanol. All materials are stable for (at least) several months.
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