RESUMO
Iridium(iii) cyclometalated complexes in aqueous solution often display relatively weak luminescence. It has been shown in previous work that this emission can be significantly enhanced (by up to two orders of magnitude) by encapsulation in cucurbit[10]uril (Q[10]). Luminescence lifetime measurements suggest a dynamic self-quenching mechanism is active, possibly due to displacement of an excited guest complex via collision with an unbound complex. We devise a model for the association of a group of iridium(iii) cyclometalated complexes with Q[10]. The model parameters are then fitted to steady-state emission titration curves. The excellent agreement of experimental data with the model provides valuable mechanistic information relating to the way this class of metal complexes interact and associate with the Q[10] host.
RESUMO
The weaker emission typically seen for iridium(III) cyclometalated complexes in aqueous medium can be reversed via encapsulation in cucurbit[10]uril (Q[10]). The Q[10] cavity is shown to effectively maximize quantum yields for the complexes, compared to any other medium. This may provide significant advantages for a number of sensor applications. NMR studies show that the complexes are accommodated similarly within the host molecule, even with cationic substituents attached to the ppy ligands, indicating that the hydrophobic effect is the dominant driving force for binding. Cavity-encapsulated 1:1 host-guest species dominate the emission, but 1:2 species are also indicated, which also give some enhancement of intensity. Results demonstrate that the enhancement is due primarily to much lower rates of nonradiative decay but also suggest that the encapsulation can cause a change in character of the emitting state.
RESUMO
A new high-nitrogen molecule, identified as azoxytriazolone (AZTO), has been generated in high yield by electroreduction of acidic aqueous solutions of nitrotriazolone (NTO). The near-quantitative conversion appears to be driven by the low solubility of the product. AZTO precipitates readily, leaving the solution virtually free of organic material, and the process may therefore present an efficient and productive remediation method for wastewater from NTO manufacture. The chemical formula and molecular structure of AZTO indicate that it may be effective as an insensitive explosive.
Assuntos
Nitrocompostos/química , Triazóis/química , Poluição Química da Água , Purificação da Água , Eletroquímica , Biologia MolecularRESUMO
Laboratory studies show that electrochemical oxidation of acidic nitrotriazolone (NTO) solutions results in complete mineralization, with ammonium nitrate as the only solution product Other products (carbon dioxide, carbon monoxide, and nitrous oxide) are eliminated as gases from the working electrode. No additional chemical loading is required for the process, and electricity isthe only input The process maytherefore represent a cost-effective and environmentally friendly method of remediation for wastewater from NTO manufacture. Electrolyses were carried out at different applied voltages and at NTO concentrations of 0.01 and 0.05 mol/L, and the results indicate that a higher oxidation rate results in a greater charge passed per mole of NTO oxidized and increased production of nitrous oxide. Mechanisms are proposed on the basis of competing oxidative pathways that account for all products formed and the total charge passed during the reaction.