Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results sh...Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.展开更多
Gas-phase hydrogen abstraction reactions have been compared using the popular density functional theory （DFT） functional BHandHLYP/aug-cc-pVTZ/RECP level of theory, on the basis of the model reaction CHCI-/CCl2- ＋ ...Gas-phase hydrogen abstraction reactions have been compared using the popular density functional theory （DFT） functional BHandHLYP/aug-cc-pVTZ/RECP level of theory, on the basis of the model reaction CHCI-/CCl2- ＋ CX3H （X = F, Cl, Br and I）. Our theoretical findings suggest the efficiency of the H-abstraction reactions induced by either CHCl- or CCl2- increases as the substrate is changed from CF3H to Cl3H, and that CHCI＇-has a higher activity in hydrogen abstraction than CCl2- for a given substrate. The entropy effect at 298 K does not significantly change the trend in reactivity of the various reactions, which is in general controlled by the heights of activation energies △E＂. Therefore, we have explored the origin of the energy barriers △E＂ of the reactions using the activation strain model of chemical reactivity.展开更多
文摘Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.
基金the Fundamental Research Funds for the Central Universities (zyz2011059)
文摘Gas-phase hydrogen abstraction reactions have been compared using the popular density functional theory （DFT） functional BHandHLYP/aug-cc-pVTZ/RECP level of theory, on the basis of the model reaction CHCI-/CCl2- ＋ CX3H （X = F, Cl, Br and I）. Our theoretical findings suggest the efficiency of the H-abstraction reactions induced by either CHCl- or CCl2- increases as the substrate is changed from CF3H to Cl3H, and that CHCI＇-has a higher activity in hydrogen abstraction than CCl2- for a given substrate. The entropy effect at 298 K does not significantly change the trend in reactivity of the various reactions, which is in general controlled by the heights of activation energies △E＂. Therefore, we have explored the origin of the energy barriers △E＂ of the reactions using the activation strain model of chemical reactivity.
