A novel sulfur-nitrogen Pi-heterocyclic radical anion, (6H-1,2,3-benzodithiazo16-ylidene)malononitrilidyl, and its homo- and heterospin salts

A novel sulfur-nitrogen Pi-heterocyclic radical anion, (6H-1,2,3-benzodithiazo16-ylidene)malononitrilidyl, and its homo- and heterospin salts Full article

Journal

Polyhedron
ISSN: 0277-5387

Output data

Year: 2014, Volume: 72, Pages: 43-49 Pages count : DOI: 10.1016/j.poly.2014.01.027

Tags

Radical anions; Sulfur-nitrogen heterocycles; X-ray diffraction; EPR spectroscopy; OFT calculations; Cyclic voltammetry; Magnetic properties

Authors

Makarov Alexander Yu. ¹ , Chulanova Elena A. ^2,3 , Semenov Nikolay A. ¹ , Pushkarevsky Nikolay A. ^3,4 , Lonchakov Anton V. ² , Bogomyakov Artem S. ⁵ , Irtegova Irina G. ¹ , Vasilieva Nadezhda V. ¹ , Lork Enno ⁶ , Gritsan Nina P. ^2,7 , Konchenko Sergey N. ^3,4 , Ovcharenko Victor I. ⁵ , Zibarev Andrey V. ^1,7

Affiliations

1	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Siberian Branch, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Nat Sci, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Inst Inorgan Chem, Siberian Branch, Novosibirsk 630090, Russia
5	(Данные Web of science) Russian Acad Sci, Int Tomog Ctr, Siberian Branch, Novosibirsk 630090, Russia
6	(Данные Web of science) Univ Bremen, Inst Inorgan Chem, D-28334 Bremen, Germany
7	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Phys, Novosibirsk 630090, Russia

(6H-1,2,3-Benzodithiazol-6-ylidene)malononitrile (4) was electrochemically and chemically reduced with tetrakis(dimethylamino)ethylene (TDAE) and CrTo1(2) into the title radical anion (5). The electrochemically generated 5 and its salts [TDAE](2+)[5](2) (7) and [CrTol(2)]* [5] (8) were characterized by solution EPR in combination with UV-Vis spectroscopy. Salts 7 and 8 were isolated and characterized by elemental analysis and solid-state EPR, and 8 by magnetic measurements in the temperature range 2-300 K. The value of the effective magnetic moment of the salt 8 at 300 K, mu eff = 1.64 (mu B), indicates n-dimerization of 5 in the solid state. For the molar magnetic susceptibility x of 8, the temperature dependences of xT and 1/ x in the range 2-300 K can be approximated by the Curie-Weiss law with the Curie-Weiss constant C and temperature 1', equal to 0.33 0.01 cm3 K mo1-1 and -1.0 0.1 K, respectively. In the mean-field approximation, the effective value of the exchange interaction of [CrTol(2)]C with its neighboring cations can be estimated as 41= -1.4 cm-1. All the experimental results were supported by DFT calculations. (C) 2014 Elsevier Ltd. All rights reserved.

Makarov A.Y. , Chulanova E.A. , Semenov N.A. , Pushkarevsky N.A. , Lonchakov A.V. , Bogomyakov A.S. , Irtegova I.G. , Vasilieva N.V. , Lork E. , Gritsan N.P. , Konchenko S.N. , Ovcharenko V.I. , Zibarev A.V.
A novel sulfur-nitrogen Pi-heterocyclic radical anion, (6H-1,2,3-benzodithiazo16-ylidene)malononitrilidyl, and its homo- and heterospin salts
Polyhedron. 2014. V.72. P.43-49. DOI: 10.1016/j.poly.2014.01.027 WOS Scopus

Published print:

Apr 1, 2014

Web of science	WOS:000334140700006
Scopus	2-s2.0-84894129754
OpenAlex	W1983902167