Synthesis and Properties of the Heterospin (S-1 = S-2=1/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

Synthesis and Properties of the Heterospin (S-1 = S-2=1/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl Научная публикация

Журнал

Inorganic Chemistry
ISSN: 0020-1669

Вых. Данные

Год: 2015, Том: 54, Номер: 14, Страницы: 7007-7013 Страниц : 7 DOI: 10.1021/acs.inorgchem.5b01033

Авторы

Pushkarevsky Nikolay A. ^1,5 , Semenov Nikolay A. ² , Dmitriev Alexey A. ^3,6 , Kuratieva Natalia V. ^1,5 , Bogomyakov Artem S. ⁴ , Irtegova Irina G. ^2,5 , Vasilieva Nadezhda V. ² , Bode Bela E. ^7,8 , Gritsan Nina P. ^3,6 , Konstantinova Lidia S. ⁹ , Woollins J.Derek ^7,8 , Rakitin Oleg A. ⁹ , Konchenko Sergey N. ^1,5 , Ovcharenko Victor I. ⁴ , Zibarev Andrey V. ^2,6,10

Организации

1	(Данные Web of science) Russian Acad Sci, Inst Inorgan Chem, 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 Chem Kinet & Combust, 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 Nat Sci, Novosibirsk 630090, Russia
6	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
7	(Данные Web of science) Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland
8	(Данные Web of science) Univ St Andrews, Ctr Magnet Resonance, St Andrews KY16 9ST, Fife, Scotland
9	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Moscow 119991, Russia
10	(Данные Web of science) Tomsk State Univ, Dept Chem, Tomsk 634050, Russia

Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes(2) (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S-1 = S-2 = 1/2) radical-ion salt [MoMes(2)](+)[1](-) (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45 degrees, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 mu(B) (theoretically expected 2.45 mu(B)) and monotonically decreases with lowering of the temperature. In the temperature range 2-300 K, the molar magnetic susceptibility of 2 is well-described by the Curie Weiss law with parameters C and theta equal to 0.78 cm(3) K mol(-1) and -31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol(2)](+)[1](-) and [CrCp2*]+[1](-), i.e., changing the cation [MAr2](+) 3d atom M = Cr (Z = 24) with weak spin orbit coupling (SO C) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol(2) (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.

Pushkarevsky N.A. , Semenov N.A. , Dmitriev A.A. , Kuratieva N.V. , Bogomyakov A.S. , Irtegova I.G. , Vasilieva N.V. , Bode B.E. , Gritsan N.P. , Konstantinova L.S. , Woollins J.D. , Rakitin O.A. , Konchenko S.N. , Ovcharenko V.I. , Zibarev A.V.
Synthesis and Properties of the Heterospin (S-1 = S-2=1/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

Inorganic Chemistry. 2015. V.54. N14. P.7007-7013. DOI: 10.1021/acs.inorgchem.5b01033 WOS Scopus РИНЦ

Полный текст от издателя

Опубликована online:	29 июн. 2015 г.
Опубликована в печати:	20 июл. 2015 г.

Web of science	WOS:000358549300039
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РИНЦ	23992052
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