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
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