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Room-temperature synthesis of CuInQ2 (Q = S or Se) in non-aqueous solution using an organoindium reagent

We have discovered a novel two-phase synthesis of CuInSe2 at 25 deg C from Cu2Se and (C5H5)3In in 4-methylpyridine (4-MePy). An analogous reaction to produce CuInS2 must be run at 140 deg C in refluxing 4-MePy in the presence of 2-mercaptopyridine. Microscopy of CuInSe2 produced at 25 deg C shows it to be platelet-shaped crystallites with an approximate particle size of 10 microns, less than 2 percent C and H, with a small amount of unidentified crystalline impurity. Our results demonstrate that it is possible to produce from solution a material that is ordinarily synthesized in bulk or films at much higher temperatures or using extraneous reagents and/or electrons.

Hepp, Aloysius F.↗

Mechanical Alloying for Making Thermoelectric Compounds

An economical room-temperature mechanical alloying process has been shown to be an effective means of making a homogeneous powder that can be hot-pressed to synthesize a thermoelectric material having reproducible chemical composition. The synthesis of a given material consists of the room temperature thermomechanical-alloying process followed b y a hot-pressing process. Relative to synthesis of nominally the same material by a traditional process that includes hot melting, this s ynthesis is simpler and yields a material having superior thermoelect ric properties.

Huang, Chen-Kuo↗

Synthesis and Characterization of Ru(II) Tris(1,1O-phenanthroline)-Electron Acceptor Dyads Incorporating the 4-benzoyl-N-methylpyridinium Cation or N-Benzyl-N'-methyl-viologen. Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Optical Oxygen Sensors

The title compounds (1 and 2, above) were synthesized by Sonogashira coupling reactions of appropriate Ru(1I) complexes with the electron a cceptors. Characterization was conducted in solution and in frozen ma trices. Finally, the title compounds were evaluated as dopants of sol-gel materials. It was found that the intramolecular quenching efficie ncy of 4-benzoyl-Nmethylpyridinium cation in solution depends on the solvent: photoluminescence is quenched completely in CH,CN, but not i n methanol or ethanol. On the other hand, intramolecular emission que nching by 4-benzyl-N-methyl viologen is complete in all solvents. The difference between the two quenchers is traced electrochemically to t he solvation of the 4-benzoyl-Nmethylpyridiniums by alcohol. In froze n matrices or adsorbed on the surfaces of silica aerogel, both Ru(I1) complex/electron acceptor dyads of this study are photoluminescent, and the absence of quenching has been traced to the environmental rigi dity. When doped aerogels are cooled at 77 K, the emission intensity increases by approximately 4x, and the spectra shift to the blue, analogous to what is observed with Ru(I1) complexes in solutions undergoi ng fluid-to-rigid transition. However, in contrast to frozen solution s, the luminescent moieties in the bulk of aerogels kept at low tempe ratures are still accessible to gas-phase quenchers diffusing through the mesopores, leading to more sensitive platforms for sensors than o ther room-temperature configurations. Thus the photoluminescence of o ur Ru(I1) complex dyads adsorbed on aerogel is quenchable by O2 both at room temperature and at 77 K. Furthermore, it was also found that O 2 modulates the photoluminescence of aerogels doped with 4-benzoyl -N -methylpyridinium-based dyads over a wider dynamic range compared wi th aerogels doped with either our vislogen-based dyads or with Ru(I1) tris(1,lO-phenanthroline) itself.

Leventis, Nicholas↗