EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge

被引：17
|
作者：
Gromov, O. I. [1 ]
Golubeva, E. N. [1 ]
Khrustalev, V. N. [2 ]
Kalai, T. [3 ]
Hideg, K. [3 ]
Kokorin, A. I. [4 ]
机构：
[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow, Russia
[2] Russian Acad Sci, Inst Organoelement Cpds, Moscow, Russia
[3] Univ Pecs, Inst Organ & Med Chem, H-7602 Pecs, Hungary
[4] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow, Russia
来源：
APPLIED MAGNETIC RESONANCE | 2014年 / 45卷 / 10期
基金：
俄罗斯基础研究基金会;
关键词：
TRANSITION-METAL DIMERS; SPIN-EXCHANGE; MAGNETIC-PROPERTIES; IONIC LIQUIDS; BEHAVIOR; SOLVENTS;
D O I：
10.1007/s00723-014-0573-z
中图分类号：
O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号：
070203 ; 070304 ; 081704 ; 1406 ;
摘要：
Two short nitroxide biradicals of similar composition, R6'aEuro"R6' (B0) and R6'aEuro"(C a parts per thousand C)-R6' (B1), where R6' is 1-oxyl-2,2,6,6-tetramethyl-3,4-ene-nitroxide ring, have been investigated by electron paramagnetic resonance spectroscopy and X-ray structural analysis. Quantum chemical calculations at UDFT/B3LYP/cc-pVDZ level were also performed and compared with the X-ray structural data. Zero-field splitting parameters D for B0 and B1 were found to be equal -0.0048 and -0.0022 cm(-1), respectively, in good agreement with quantum chemical prediction. Potential energy surface scans corresponding to pathways of the conformational rearrangements were calculated; rotation barriers for B0 and B1 were found to be 19.2 and 4.0 kJ/mol, respectively; and structural rigidity and probable differences in biradicals behavior are discussed. Calculations of spin density distribution in biradicals B0 and B1 were also carried out.
引用
收藏
页码：981 / 992
页数：12
相关论文
共 50 条
  • [1] EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge
    O. I. Gromov
    E. N. Golubeva
    V. N. Khrustalev
    T. Kálai
    K. Hideg
    A. I. Kokorin
    Applied Magnetic Resonance, 2014, 45 : 981 - 992
  • [2] Spin Density Distribution in a Nitroxide Biradical Containing 13C-Enriched Acetylene Groups in the Bridge: DFT Calculations and EPR Investigation
    Kokorin, A. I.
    Zaripov, R. B.
    Gromov, O. I.
    Sukhanov, A. A.
    Kalai, T.
    Lamperth, E.
    Hideg, K.
    APPLIED MAGNETIC RESONANCE, 2016, 47 (09) : 1057 - 1067
  • [3] Spin Density Distribution in a Nitroxide Biradical Containing 13C-Enriched Acetylene Groups in the Bridge: DFT Calculations and EPR Investigation
    A. I. Kokorin
    R. B. Zaripov
    O. I. Gromov
    A. A. Sukhanov
    T. Kálai
    É. Lamperth
    K. Hideg
    Applied Magnetic Resonance, 2016, 47 : 1057 - 1067
  • [4] The Structure and EPR Behavior of Nitroxide Biradical Containing Phosphorus Atom in the Bridge
    Kokorin, Alexander I.
    Khrustalev, Victor N.
    Gromov, Oleg I.
    APPLIED MAGNETIC RESONANCE, 2015, 46 (12) : 1429 - 1442
  • [5] The Structure and EPR Behavior of Nitroxide Biradical Containing Phosphorus Atom in the Bridge
    Alexander I. Kokorin
    Victor N. Khrustalev
    Oleg I. Gromov
    Applied Magnetic Resonance, 2015, 46 : 1429 - 1442
  • [6] The Structure and Internal Dynamics of R6-p-C6H4-R6 Biradical: EPR, X-ray Crystallography and DFT Calculations
    A. I. Kokorin
    O. I. Gromov
    P. V. Dorovatovskii
    V. A. Lazarenko
    V. N. Khrustalev
    K. Hideg
    T. Kálai
    Applied Magnetic Resonance, 2019, 50 : 425 - 439
  • [7] The Structure and Internal Dynamics of R6-p-C6H4-R6 Biradical: EPR, X-ray Crystallography and DFT Calculations
    Kokorin, A. I.
    Gromov, O. I.
    Dorovatovskii, P. V.
    Lazarenko, V. A.
    Khrustalev, V. N.
    Hideg, K.
    Kalai, T.
    APPLIED MAGNETIC RESONANCE, 2019, 50 (1-3) : 425 - 439
  • [8] X-ray and DFT calculations of novel spiroisoxazolines derivatives
    Moumou, Mohamed
    Outahar, Fatima
    Akssira, Mohamed
    Benharref, Ahmed
    Saadi, Mohamed
    El Ammari, Lahcen
    Ketatni, El Mostafa
    JOURNAL OF MOLECULAR STRUCTURE, 2022, 1264
  • [9] Nitronyl Nitroxide Radicals Linked to Exchange-Coupled Metal Dimers - Studies Using X-ray Crystallography, Magnetic Susceptibility Measurements, EPR Spectroscopy, and DFT Calculations
    Jung, Martin
    Sharma, Ajay
    Hinderberger, Dariush
    Braun, Sebastian
    Schatzschneider, Ulrich
    Rentschler, Eva
    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (11) : 1495 - 1502
  • [10] Is bis(trifluoromethylsulfonyl)amide an innocent anion? X-Ray structure data and DFT calculations
    Illner, Peter
    Puchta, Ralph
    Heinemann, Frank W.
    van Eldik, Rudi
    DALTON TRANSACTIONS, 2009, (15) : 2795 - 2801
12345