Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts
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10.1039/C9NJ04069B

Selenium & Tellurium chemistry at the beginning of the 3rd millennium: a celebration of ICCST


В журнале New Journal of Chemistry, 2019, Vol. 43, N 41, Pp. 16331-16-337,  (IF 3,069) опубликована статья с участием сотрудников Института:   к.х.н. Н.А. Семёнова, Е.А. Радюш, Е.А. Чулановой, д.х.н. И.Ю. Багрянской, к.х.н. Иртеговой, д.х.н. Л.А. Шундрина и д.х.н. А.В. Зибарева

Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts

Nikolay A. Semenov, Ekaterina A. Radiush, Elena A. Chulanova, Alexandra M. Z. Slawin, J. Derek Woollins, Evgeny M. Kadilenko, Irina Yu. Bagryanskaya, Irina G. Irtegova, Artem S. Bogomyakov, Leonid A. Shundrin, Nina P. Gritsan and Andrey V. Zibarev

New Journal of Chemistry, First published: 12 Sptember 2019

doi: 10.1039/C9NJ04069B

2019_NJC_41_Semenov

 

Abstract

5,6-Dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine 1 was synthesized and electrochemically and chemically reduced into its radical anion [1]˙−, which was characterized by EPR spectroscopy and DFT calculations, and isolated in the form of homospin salts [K(18-crown-6)]+[1]˙− (2) and [Na(18-crown-6)]+[1]˙− (3). The crystal structure of 2 revealed π-dimers of [1]˙− featuring a shortened interplanar separation of 3.18 Å, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the π-dimers of [1]˙− suggest a closed-shell singlet ground state with a noticeable contribution of diradical character. According to EPR and SQUID magnetometry, salt 2 is diamagnetic in the range of 2–300 K, whereas salt 3 is paramagnetic and reveals weak antiferromagnetic exchange interactions.

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