RESUMO
Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4- (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4- (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3- for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4- (Ru-N3); (ii) [PW11O39{RuIII(N4HC-CH3)}]4- (Ru-Tz) as a click-reaction product; and (iii) [PW11O39{RuII(N2)}]5- (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.
Assuntos
Complexos de Coordenação/química , Ligantes , Rutênio/química , Azidas/química , Estrutura Molecular , Espectroscopia Fotoeletrônica , Espectrometria de Massas por Ionização por Electrospray , Compostos de Tungstênio/químicaRESUMO
The atomic structure of antiphase boundaries in Sr-doped lanthanum scandate (La1-xSrxScO3-δ) perovskite, promising as the proton conductor, was modelled by means of DFT method. Two structural types of interfaces formed by structural octahedral coupling were constructed: edge- and face-shared. The energetic stability of these two interfaces was investigated. The mechanisms of oxygen vacancy formation and migration in both types of interfaces were modelled. It was shown that both interfaces are structurally stable and facilitate oxygen ionic migration. Oxygen vacancy formation energy in interfaces is lower than that in the regular structure, which favours the oxygen vacancy segregation within such interfaces. The calculated energy profile suggests that both types of interfaces are advantageous for oxygen ion migration in the material.