Author:
Buta Maria Cristina,Toader Ana Maria,Frecus Bogdan,Oprea Corneliu I.,Cimpoesu Fanica,Ionita Gabriela
Abstract
Nitroxide-based radicals, having the advantage of firm chemical stability, are usable as probes in the detection of nanoscale details in the chemical environment of various multi-component systems, based on subtle variations in their electron paramagnetic resonance spectra. We propose a systematic walk through the vast area of problems and inquires that are implied by the rationalization of solvent effects on the spectral parameters, by first-principle methods of structural chemistry. Our approach consists of using state-of-the-art procedures, like Density Functional Theory (DFT), on properly designed systems, kept at the border of idealization and chemical realism. Thus, we investigate the case of real solvent molecules intervening in different configurations between two radical molecules, in comparison with radicals taken in vacuum or having the solvent that is treated by surrogate models, such as polarization continuum approximation. In this work, we selected the dichloromethane as solvent and the prototype radicals abbreviated TEMPO ((2,2,6,6-Tetramethylpiperidin-1-yl) oxyl). In another branch of the work, we check the interaction of radicals with large toroidal molecules, β-cyclodextrin, and cucurbit[6]uril, modeling the interaction energy profile at encapsulation. The drawn synoptic view offers valuable rationales for understanding spectroscopy and energetics of nitroxide radicals in various environments, which are specific to soft chemistry.
Funder
Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Computer Science Applications,Spectroscopy,Molecular Biology,General Medicine,Catalysis
Cited by
6 articles.
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