RESUMO
Equation-of-state (pressure, density, temperature, internal energy) and reflectivity measurements on shock-compressed CO_{2} at and above the insulating-to-conducting transition reveal new insight into the chemistry of simple molecular systems in the warm-dense-matter regime. CO_{2} samples were precompressed in diamond-anvil cells to tune the initial densities from 1.35 g/cm^{3} (liquid) to 1.74 g/cm^{3} (solid) at room temperature and were then shock compressed up to 1 TPa and 93 000 K. Variation in initial density was leveraged to infer thermodynamic derivatives including specific heat and Gruneisen coefficient, exposing a complex bonded and moderately ionized state at the most extreme conditions studied.
RESUMO
The redox behavior was evaluated for several (BIPY)Cu(I) complexes (BIPY = 2,2'-bipyridyl) with unsaturated ligands by means of cyclic voltammetry in CH2Cl2 at reduced temperatures (-78 degrees, -23 degrees, 0 degree C). The complexes studied are [Cu(I)(BIPY)(C2H4)]PF6, [Cu(I)(BIPY)(3-hexyne)] PF6, [Cu(I)(BIPY)(DEAD)]PF6, ([Cu(I)(BIPY)]2 DEAD)[PF6]2 (DEAD = diethyl acetylene dicarboxylate) and [Cu(I)(BIPY)(CH3CN)]PF6. The oxidations are quasi-reversible at -78 degrees C for scan rates of 20 to 200 mV/sec. The reductions were irreversible on the CV time scale. Evidence is presented in support of a role for an electron transfer mechanism in the case of the plant hormone ethylene. Related literature data are also discussed.
