ELECTRONIC STRUCTURE OF FUNCTIONALIZED THIA- AND CALIX[4]ARENES
L. N. Mazalov1,2, S. A. Lavrukhina1, A. D. Fedorenko1, G. I. Semushkina1, A. V. Kalinkin3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia 3Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: рентгеновская эмиссионная спектроскопия, рентгеновская фотоэлектронная спектроскопия, квантово-химические расчеты, метод DFT, каликс[4]аренфосфиноксиды, тиакаликс[4]аренфосфиноксиды, экстрагент, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, quantum chemical calculations, DFT method, calix[4]arene phosphine oxides, thiacalix[4]arene phosphine oxides, extractant
Abstract
The electronic structure of calix[4]arene phosphine oxides (CPO) and thiacalix[4]arene phosphine oxides (TCPO) is studied by X-ray photoelectron and emission spectroscopy and quantum chemical methods. The electron density distribution over atoms contained in CPO and ТCPO is analyzed. The structure of higher occupied molecular orbitals (HOMO) is examined. It is shown that HOMOs of these compounds mainly consist of contributions of oxygen 2 p atomic orbitals (AOs) of phosphoryl and hydroxyl moieties and also bridging sulfur 3 p АОs, which indicates the bifunctionality of the considered extractant molecules. The mutual effect of the lower and upper rims of CPOs and ТCPOs as well as the effect of their structures on the electron density distribution over calixarene molecules is investigated
|