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, Andrey V. Zibarev

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)16331-16337
Number of pages7
JournalNew Journal of Chemistry
Volume43
Issue number41
DOIs
Publication statusPublished - 7 Nov 2019

Keywords

  • STATE PERTURBATION-THEORY
  • RADICAL-ANION SALTS
  • CRYSTAL-STRUCTURE
  • HETEROSPIN S-1
  • VALENCE
  • IMPLEMENTATION

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