Home About us Contact
|
Home About us Contact | ||
|
|
||
NO2 Group (no2 + group)
Selected AbstractsKinetic study of the reactions of oxoiron(IV) with aromatic substrates in aqueous solutions,INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2002Daniel O. Mártire The kinetics of the reactions of oxoiron(IV) (FeO2+) with phenol, nitrobenzene, m -, o -, and p -nitrophenol in 1 M HClO4 was investigated by the stopped-flow technique. The rate constants of these reactions decrease with increasing the one-electron reduction potentials of the corresponding radical cations of the substrates and with the Hammett parameter of the NO2 group in the phenol ring. A reaction mechanism is proposed, which accounts for the observed trends and for the nature of the reaction products. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 488,494, 2002 [source] Band gaps and the possible effect on impact sensitivity for some nitro aromatic explosive materialsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2009Hong Zhang Abstract The first principle density functional theory method SIESTA has been used to compute the band gap of several polynitroaromatic explosives, such as TATB, DATB, TNT, and picric acid. In these systems, the weakest bond is the one between an NO2 group and the aromatic ring. The bond dissociation energy (BDE) alone cannot predicate the relative sensitivity to impact of these four systems correctly. It was found that their relative impact sensitivity could be explained by considering the BDE and the band gap value of the crystal state together. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] High-performance liquid chromatography with electrospray ionisation mass spectrometry and diode array detection in the identification and quantification of the degradation products of calix[4]arene crown-6 under radiolysisRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2004C. Lamouroux The extraction of 135Cs from high-activity liquid waste, arising from reprocessing of spent nuclear fuel, can be achieved by using calix[4]arene crown-6 compounds. The radiolytic degradation of di(n-octyloxy)calix[4]arene crown-6 (octMC6), in aliphatic or aromatic solvent in contact with 3 M nitric acid, was studied by high-performance liquid chromatography directly coupled to electrospray ionisation mass spectrometry (LC/ESI-MS). More than 50 distinct degradation products were observed, and about 30 of these were identified. These compounds can be assigned to three categories, namely, products of reactions involving radical cleavage or addition, of oxidation reactions, or of aromatic substitution reactions. The major product, corresponding to substitution by an NO2 group, was quantified by external standard calibration using a purified synthetic sample. Despite the observation of all these degradation compounds, octMC6 appears to be remarkably stable under these drastic conditions, combining hydrolysis (HNO3 3,M) and an extreme exposure to radiolysis (106,Gy). Less than 35% degradation of octMC6 was observed in aromatic solvent under these conditions. Copyright © 2004 John Wiley & Sons, Ltd. [source] Cyclometalated IrIII Complexes with Substituted 1,10-Phenanthrolines: A New Class of Efficient Cationic Organometallic Second-Order NLO ChromophoresCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2010Adriana Valore Dr. Abstract Cyclometalated cationic IrIII complexes with substituted 1,10-phenanthrolines (1,10-phen), such as [Ir(ppy)2(5-R-1,10-phen)]Y (ppy=cyclometalated 2-phenylpyridine; R=NO2, H, Me, NMe2; Y,=PF6,, C12H25SO3,, I,) and [Ir(ppy)2(4-R,7-R-1,10-phen)]Y (R=Me, Ph) are characterized by a significant second-order optical non linearity (measured by the electrical field induced second harmonic generation (EFISH) technique). This nonlinearity is controlled by MLCT processes from the cyclometalated IrIII, acting as a donor push system, to ,* orbitals of the phenanthroline, acting as an acceptor pull system. Substitution of cyclometalated 2-phenylpyridine by the more , delocalized 2-phenylquinoline (pq) or benzo[h]quinoline (bzq) or by the sulfur-containing 4,5-diphenyl-2-methyl-thiazole (dpmf) does not significantly affect the ,, absolute value, which instead is affected by the nature of the R substituents on the phenanthroline, the higher value being associated with the electron-withdrawing NO2 group. By using a combined experimental (the EFISH technique and 1H and 19F PGSE NMR spectroscopy) and theoretical (DFT, time-dependent-DFT (TDDFT), sum over states (SOS) approach) investigation, evidence is obtained that ion pairing, which is controlled by the nature of the counterion and by the concentration, may significantly affect the ,, values of these cationic NLO chromophores. In CH2Cl2, concentration-dependent high absolute values of ,, are obtained for [Ir(ppy)2(5-NO2 -1,10-phen)]Y if Y is a weakly interacting anion, such as PF6,, whereas with a counterion, such as C12H25SO3, or I,, which form tight ion-pairs, the absolute value of ,, is lower and quite independent of the concentration. This ,, trend is partially due to the perturbation of the counterion on the LUMO ,* levels of the phenanthroline. The correlation between the ,, value and dilution shows that the effect of concentration is a factor that must be taken into careful consideration. [source] | ||||||||||