Bis(toluene)chromium(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl and [1,2,5]Thiadiazolo[3,4-b]pyrazinidyl: New Heterospin (S-1 = S-2=1/2) Radical-Ion Salts

Bis(toluene)chromium(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl and [1,2,5]Thiadiazolo[3,4-b]pyrazinidyl: New Heterospin (S-1 = S-2=1/2) Radical-Ion Salts Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2013, Volume: 52, Number: 11, Pages: 6654-6663 Pages count : 10 DOI: 10.1021/ic400659q

Authors

Semenov Nikolay A. ¹ , Pushkarevsky Nikolay A. ^2,5 , Suturina Elizaveta A. ^3,6 , Chulanova Elena A. ^3,5 , Kuratieva Natalia V. ² , Bogomyakov Artem S. ⁴ , Irtegova Irina G. ¹ , Vasilieva Nadezhda V. ¹ , Konstantinova Lidia S. ⁷ , Gritsan Nina P. ^3,6 , Rakitin Oleg A. ⁷ , Ovcharenko Victor I. ⁴ , Konchenko Sergey N. ² , Zibarev Andrey V. ^1,6

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 Inorgan Chem, Siberian Branch, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Siberian Branch, 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, Natl Res Univ, Dept Nat Sci, Novosibirsk 630090, Russia
6	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Phys, Novosibirsk 630090, Russia
7	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Moscow 119991, Russia

Bis(toluene)chromium(0), Cr-0(eta(6)-C7H8)(2) (3), readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) and [1,2,5]thiadiazolo[3,4-b]pyrazine (2) in a tetrahydrofuran solvent with the formation of heterospin, S-1 = S-2 = 1/2, radical-ion salts [3](+)[1](-) (4) and [3](+)[2](-) (5) isolated in high yields. The salts 4 and 5 were characterized by single-crystal X-ray diffraction (XRD), solution and solid-state electron paramagnetic resonance, and magnetic susceptibility measurements in the temperature range 2-300 K. Despite the formal similarity of the salts, their crystal structures were very different and, in contrast to 4, in 5 anions were disordered. For the XRD structures of the salts, parameters of the Heisenberg spin Hamiltonian were calculated using the CASSCF/NEVPT2 and broken-symmetry density functional theory approaches, and the complex magnetic motifs featuring the dominance of antiferromagnetic (AF) interactions were revealed. The experimental chi T temperature dependences of the salts were simulated using the Van Vleck formula and a diagonalization of the matrix of the Heisenberg spin Hamiltonian for the clusters of 12 paramagnetic species with periodic boundary conditions. According to the calculations and chi T temperature dependence simulation, a simplified magnetic model can be suggested for the salt 4 with AF interactions between the anions ([1](-)...[1](-), J(1) = -5.77 cm(-1)) and anions and cations ([1](-)...[3](+), J(2) = -0.84 cm(-1)). The magnetic structure of the salt 5 is much more complex and can be characterized by AF interactions between the anions, [2](-)...[2](-), and by both AF and ferromagnetic (FM) interactions between the anions and cations, [2](-)...[3](+). The contribution from FM interactions to the magnetic properties of the salt 5 is in qualitative agreement with the positive value of the Weiss constant Theta (0.4 K), whereas for salt 4, the constant is negative (-7.1 K).

Semenov N.A. , Pushkarevsky N.A. , Suturina E.A. , Chulanova E.A. , Kuratieva N.V. , Bogomyakov A.S. , Irtegova I.G. , Vasilieva N.V. , Konstantinova L.S. , Gritsan N.P. , Rakitin O.A. , Ovcharenko V.I. , Konchenko S.N. , Zibarev A.V.
Bis(toluene)chromium(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl and [1,2,5]Thiadiazolo[3,4-b]pyrazinidyl: New Heterospin (S-1 = S-2=1/2) Radical-Ion Salts
Inorganic Chemistry. 2013. V.52. N11. P.6654-6663. DOI: 10.1021/ic400659q WOS Scopus РИНЦ

Published online:	May 21, 2013
Published print:	Jun 3, 2013

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