Heterospin π-heterocyclic radical-anion salt: Synthesis, structure, and magnetic properties of decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c ][1,2,5]thiadiazolidyl

Nikolay A. Semenov, Nikolay A. Pushkarevsky, Anton V. Lonchakov, Artem S. Bogomyakov, Elena A. Pritchina, Elizaveta A. Suturina, Nina P. Gritsan, Sergey N. Konchenko, Ruediger Mews, Victor I. Ovcharenko, Andrey V. Zibarev

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33 Citations (Scopus)

Abstract

Decamethylchromocene, CrII5-C 5(CH3)5)2 (2), readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) in a tetrahydrofuran solvent at ambient temperature with the formation of radical-anion salt [2] +[1]- (3) isolated in 97% yield. The heterospin salt 3 ([2]+, S = 3/2; [1]-, S = 1/2) was characterized by single-crystal X-ray diffraction as well as magnetic susceptibility measurements in the temperature range 2-300 K. The experimental data together with theoretical analysis of the salt-s magnetic structure within the CASSCF and spin-unrestricted broken-symmetry (BS) density functional theory (DFT) approaches revealed antiferromagnetic (AF) interactions in the crystalline 3: significant between anions [1]-, weak between cations [2]+, and very weak between [1]- and [2]+. Experimental temperature dependences of the magnetic susceptibility and the effective magnetic moment of 3 were very well reproduced in the assumption of the AF-coupled [1]-⋯[1]- (J1 = -40 ± 9 cm-1) and [2]+⋯ [2]+ (J2 = -0.58 ± 0.03 cm-1) pairs. The experimental J1 value is in reasonable agreement with the value calculated using BS UB3LYP/6-31+G(d) (-61 cm-1) and CASSCF(10,10)/6-31+G(d) (-15.3 cm-1) approaches. The experimental J2 value is also in agreement with that calculated using the BS DFT approach (-0.33 cm-1).

Original languageEnglish
Pages (from-to)7558-7564
Number of pages7
JournalInorganic Chemistry
Volume49
Issue number16
DOIs
Publication statusPublished - 16 Aug 2010

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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