Heterospin pi-Heterocyclic Radical-Anion Salt: Synthesis, Structure, and Magnetic Properties of Decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

Heterospin pi-Heterocyclic Radical-Anion Salt: Synthesis, Structure, and Magnetic Properties of Decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2010, Volume: 49, Number: 16, Pages: 7558-7564 Pages count : DOI: 10.1021/ic101064c

Authors

Semenov Nikolay A. ² , Pushkarevsky Nikolay A. ³ , Lonchakov Anton V. ^1,5 , Bogomyakov Artem S. ⁴ , Pritchina Elena A. ^1,6 , Suturina Elizaveta A. ^1,5 , Gritsan Nina P. ^1,5 , Konchenko Sergey N. ³ , Mews Ruediger ⁷ , Ovcharenko Victor I. ⁴ , Zibarev Andrey V. ^2,5

Affiliations

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

Decamethylchromocene, Cr parallel to(eta(5)-C(5)(CH(3))(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 [2r, 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](-) (J(1) = -40 +/- 9 cm(-1)) and [2](+) ... [2](+)-4- (J(2) = 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 J(2) value is also in agreement with that calculated using the BS DFT approach (-0.33 cm(-1)).

Semenov N.A. , Pushkarevsky N.A. , Lonchakov A.V. , Bogomyakov A.S. , Pritchina E.A. , Suturina E.A. , Gritsan N.P. , Konchenko S.N. , Mews R. , Ovcharenko V.I. , Zibarev A.V.
Heterospin pi-Heterocyclic Radical-Anion Salt: Synthesis, Structure, and Magnetic Properties of Decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl
Inorganic Chemistry. 2010. V.49. N16. P.7558-7564. DOI: 10.1021/ic101064c WOS Scopus РИНЦ

Published online:	Jul 15, 2010
Published print:	Aug 16, 2010

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