caa a22 4500 605545626 CHVBK 20210128105200.0 cr unu---uuuuu 210128e20151201xx s 000 0 eng 10.1007/s00723-015-0716-x doi (NATIONALLICENCE)springer-10.1007/s00723-015-0716-x The Structure and EPR Behavior of Nitroxide Biradical Containing Phosphorus Atom in the Bridge [Elektronische Daten] [Alexander Kokorin, Victor Khrustalev, Oleg Gromov] Two short nitroxide biradicals of similar composition: (H5C6)O=P(OR6)2 (BP) and O=S(OR6)2 (BS), where OR6 is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, have been studied by electron paramagnetic resonance spectroscopy, and X-ray structural analysis. Variations of the intramolecular electron spin exchange in the biradicals, dissolved in toluene, as a function of temperature were characterized by changes in the isotropic 14N hyperfine splitting (hfs) constant a, values of the exchange integral |J|, and compared with the X-ray structural data. Thermodynamic parameters of the conformational rearrangements were calculated. Geometry optimization and spin density distribution calculations of biradical BP were carried out on the DFT/UB3LYPPBE0/cc-pVdTZz and DFT/ROPBE/N07D levels of theory and compared with those of BS. Probable differences in biradicals behavior are discussed. Springer-Verlag Wien, 2015 Kokorin Alexander N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation aut Khrustalev Victor A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russian Federation aut Gromov Oleg N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation aut Applied Magnetic Resonance Springer Vienna 46/12(2015-12-01), 1429-1442 0937-9347 46:12<1429 2015 46 723 https://doi.org/10.1007/s00723-015-0716-x text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00723-015-0716-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Kokorin Alexander N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Khrustalev Victor A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Gromov Oleg N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation aut NATIONALLICENCE 773 0- Applied Magnetic Resonance Springer Vienna 46/12(2015-12-01), 1429-1442 0937-9347 46:12<1429 2015 46 723 SWISSBIB 560526342