Synthesis and characterization of zinc di(O-2,2-dimethylpentan-3-yl dithiocarbonates) bearing pyridine or tetramethylethylenediamine coligands and investigation of their thermal conversion mechanisms towards nanocrystalline zinc sulfide.

Metal xanthates are versatile single source precursors for the preparation of various metal sulfides. In this study, we present the synthesis of the two novel zinc xanthate complexes bis(O-2,2-dimethylpentan-3-yl-dithiocarbonato)(N,N,N',N'-tetramethylethylenediamine)zinc(ii) and bis(O-2,2-dimethylpentan-3-yl-dithiocarbonato)(pyridine)zinc(ii). A thorough investigation of these compounds revealed distinct differences in their structural and thermal properties. While in the complex containing the chelating tetramethylethylenediamine, the xanthate groups coordinate in a monodentate way, they are bidentally coordinated to the zinc atom in the pyridine containing complex. Both compounds show a two-step thermal decomposition with an onset temperature of 151 °C and 156 °C for the tetramethylethylenediamine and pyridine containing complex, respectively. Moreover, different mechanisms are revealed for the two phases of the decomposition based on high resolution mass spectrometry investigations. By the thermal conversion process nanocrystalline zinc sulfide is produced and the coligand significantly influences its primary crystallite size, which is 4.4 nm using the tetramethylethylenediamine and 11.4 nm using the pyridine containing complex for samples prepared at a temperature of 400 °C.

Tuning the dynamic range and sensitivity of optical oxygen-sensors by employing differently substituted polystyrene-derivatives.

Ten different polystyrene-derivatives were tested with respect to their potential use as matrix materials for optical oxygen sensors in combination with the platinum(II) meso-tetra(4-fluorophenyl)tetrabenzoporphyrin as indicator dye. Either halogen atoms or bulky residues were introduced as substituents on the phenyl ring. A fine-tuning of the sensor sensitivity was achieved, without compromising solubility of the indicator in the matrix by providing a chemical environment very similar to polystyrene (PS), a standard matrix in optical oxygen sensors. To put the results into perspective, the studied materials were compared to PS regarding sensitivity of the sensor, molecular weight and glass-transition temperature. The materials promise to be viable alternatives to PS with respect to the requirements posed in various sensor application fields. Some of the polymers (e.g. poly(2,6-dichlorostyrene)) promise to be of use in applications requiring measurements from 0 to 100% oxygen due to linearity across this range. Poly(4-tert-butylstyrene) and poly(2,6-fluorostyrene), on the other hand, yield sensors with increased sensitivity. Sensor stability was evaluated as a function of the matrix, a topic which has not received a lot of interest so far.

Nonradiative deactivation of europium(III) luminescence as a detection scheme for moisture.

The nonradiative deactivation of the excited state of europium(III)-based phosphors via OH-vibrations in the presence of water allows the detection of moisture in nitrogen at concentration levels down to at least 25 ppm (0.09% RH).

Synthesis and characterization of alternating fluorene-thiophene copolymers bearing ethylene glycol side-chains.

ABSTRACT: New alternating fluorene-thiophene copolymers are introduced bearing polar ethylene glycol-carboxylate functionalities on the thiophene ring to achieve enhanced solubility in polar solvents. Suzuki polycondensation was applied to synthesize a set of three polymers with differing lengths of the ethylene glycol side-chains. The polymers are thermally stable up to temperatures of 300 °C. Solutions of the polymers in CHCl3 show an absorption maximum at approximately 397 nm and a luminescence maximum of 472 nm in solutions with quantum yield of 30%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels have been determined to be at -5.7 and -2.6 eV, respectively.

Investigation of the formation of CuInS2 nanoparticles by the oleylamine route: comparison of microwave-assisted and conventional syntheses.

The formation of copper indium disulfide nanoparticles via the oleylamine route using copper iodide, indium chloride, and elemental sulfur has been investigated by applying conventional thermal heating as well as microwave irradiation. Oleylamine thereby acts as a capping ligand as well as a solvent. In an initial set of experiments, the onset of the reaction was determined to be around 115 °C by an in situ X-ray study using Synchrotron radiation. Using comparatively low synthesis temperatures of 120 °C, it is already possible to obtain nanoparticles of 2-4 nm with both heating methods but with irregular shape and size distribution. By applying higher temperatures of 220 °C, more crystalline and larger nanoparticles were obtained with slight differences in crystallite size and size distribution depending on the synthesis route. The size of the nanoparticles is in the range of 3-10 nm depending on the heating time. Using microwave irradiation, it is possible to obtain nanoparticles in only 90 s of total synthesis time. Control experiments to probe a nonthermal microwave effect were carried out ensuring an identical experimental setup, including the heating profile, the stirring rate, and the volume and concentration of the solutions. These experiments clearly demonstrate that for the preparation of CuInS(2) nanoparticles described herein no differences between conventional and microwave heating could be observed when performed at the same temperature. The nanoparticles obtained by microwave and thermal methods have the same crystal phase, primary crystallite size, shape, and size distribution. In addition, they show no significant differences concerning their optical properties.

The stoichiometry of single nanoparticles of copper zinc tin selenide.

Cu(2)ZnSnSe(4) nanoparticles have high potential to be used as ink for printable solar cells. Using transmission electron microscopy we show that these nanoparticles exhibit a broad range of chemical heterogeneity. These results are contrary to the interpretation of previous experimental work and will have considerable impact on the development of these nanoparticles.