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ISSUE 12

Year 2007, Month 12 (Section Full Articles, Page 2364)

EPR spectroscopy of quintet 4-amino-3,5-dichloropyridine-2,6-diyldinitrene isolated in solid argon

E. Ya. Misochko, A. V. Akimov, V. F. Lavitskii, and S. V. Chapyshev

An EPR spectrum of solid Ar isolated quintet 4-amino-3,5-dichloropyridin-2,6-diyldinitrene that formed by the photolysis of 4-amino-2,6-diazido-3,5-dichloropyridine at 15 K was recorded. Using computer simulation based on numerical diagonalization of the quintet spin Hamiltonian matrices, it was established that this EPR spectrum corresponds to a quintet spin state with the magnetic parameters g = 2.0023, |Dq| = 0.2100 cm–1, and |Eq| = 0.0560 cm–1. Owing to high resolution of the experimental spectrum, the zero-field splitting parameters of the quintet intermediate were determined to an accuracy of at least 5•10–4 cm–1. Calculations of the fine-structure energy levels in external magnetic field and the dependences of the EPR signal positions and intensities of the quintet dinitrene on the direction of external magnetic field were performed for the first time. This allowed unambiguous assignment of all EPR lines of quintet molecules having both in-principal-axis and off-principal-axis orientations.

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