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. Kalai, K. Hideg, A. I. Kokorin

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Abstract

Two short nitroxide biradicals of similar composition, R6′–R6′ (B0) and R6′–(C ≡ 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.

Original languageEnglish
Pages (from-to)981-992
Number of pages12
JournalApplied Magnetic Resonance
Volume45
Issue number10
DOIs
Publication statusPublished - Oct 18 2014

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acetylene
structural stability
structural analysis
density distribution
electron paramagnetic resonance
x rays
potential energy
rings
predictions
spectroscopy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge. / Gromov, O. I.; Golubeva, E. N.; Khrustalev, V. N.; Kalai, T.; Hideg, K.; Kokorin, A. I.

In: Applied Magnetic Resonance, Vol. 45, No. 10, 18.10.2014, p. 981-992.

Research output: Contribution to journalArticle

Gromov, O. I. ; Golubeva, E. N. ; Khrustalev, V. N. ; Kalai, T. ; Hideg, K. ; Kokorin, A. I. / EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge. In: Applied Magnetic Resonance. 2014 ; Vol. 45, No. 10. pp. 981-992.
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AU - Kalai, T.

AU - Hideg, K.

AU - Kokorin, A. I.

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