Cobaltocenium [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazol idyl: Synthesis, structure, and magnetic properties

Cobaltocenium [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazol idyl: Synthesis, structure, and magnetic properties Научная публикация

Журнал

European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682

Вых. Данные

Год: 2008, Номер: 24, Страницы: 3833-3838 Страниц : 6 DOI: 10.1002/ejic.200800390

Ключевые слова

cobaltocene; magnetic properties; sulfur-nitrogen heterocycles; radical anions

Авторы

Konchenko Sergey N. , Gritsan Nina P. , Lonchakov Anton V. , Irtegova Irina G. , Mews Ruediger , Ovcharenko Victor I. , Radius Udo , Zibarev Andrey V.

Организации

1	(Данные Web of science) Russian Acad Sci, Inst Inorgan Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Novosibirsk 630090, Russia
5	(Данные Web of science) Univ Bremen, Inst Inorgan & Phys Chem, D-28334 Bremen, Germany
6	(Данные Web of science) Russian Acad Sci, Int Tomog Ctr, Novosibirsk 630090, Russia
7	(Данные Web of science) Univ Karlsruhe, Inst Inorgan Chem, D-76131 Karlsruhe, Germany

Cobaltocene, [Co(II)(eta(5)-C(5)H(5))(2)], readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl (2) to the [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl radical anion (1) which was isolated in the form of the thermally stable salt [Co(III)(eta(5)-C(5)H(5))(2)][1] (5) in 93 % yield. The XRD structure of 5 displays layers of radical anions 1, with S center dot center dot center dot N contacts of 358.2 and 366.0 pm between neighboring species. The salt was further characterized by ESR spectroscopy in the solid state as well as in solution. The temperature dependence of its magnetic susceptibility (%) in the range of 2-300 K with a maximum at (9.7 +/- 0.5) K indicates antiferromagnetic ordering of the spin system. The magnetic structure of 5 was analyzed in terms of dimeric exchange integrals calculated by a spin-unrestricted broken-symmetry approach at the DFT/UB3LYP/6-31+G(d) level of theory and was found to be 2D. Further analysis of the chi(T) dependence was performed by using the low- and high-temperature series expansion methods for the S = 1/2 square lattice antiferromagnetic Heisenberg model. The exchange interactions between radical anions 1 were estimated to be J = (-4.2 +/- 0.7) cm(-1). With the general form of the Van Vleck equation for a [3 x 4] grid of spins 1/2, the best fit of the experimental chi(T) was achieved with J(1) = -5.0cm(-1) and J(2) = -0.23(-1). Thus, the exchange interactions in 5 are stronger than those observed for previously studied salts of 1. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Konchenko S.N. , Gritsan N.P. , Lonchakov A.V. , Irtegova I.G. , Mews R. , Ovcharenko V.I. , Radius U. , Zibarev A.V.
Cobaltocenium [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazol idyl: Synthesis, structure, and magnetic properties
European Journal of Inorganic Chemistry. 2008. N24. P.3833-3838. DOI: 10.1002/ejic.200800390 WOS Scopus РИНЦ

Опубликована в печати:

1 авг. 2008 г.

Web of science	WOS:000258855900011
Scopus	2-s2.0-53249086476
РИНЦ	13577925
OpenAlex	W1976834864