TY - JOUR

T1 - Synthesis and Properties of the Heterospin (S1 = S2 = 1/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4- c ][1,2,5]thiadiazolidyl

AU - Pushkarevsky, Nikolay A.

AU - Semenov, Nikolay A.

AU - Dmitriev, Alexey A.

AU - Kuratieva, Natalia V.

AU - Bogomyakov, Artem S.

AU - Irtegova, Irina G.

AU - Vasilieva, Nadezhda V.

AU - Bode, Bela E.

AU - Gritsan, Nina P.

AU - Konstantinova, Lidia S.

AU - Woollins, J. Derek

AU - Rakitin, Oleg A.

AU - Konchenko, Sergey N.

AU - Ovcharenko, Victor I.

AU - Zibarev, Andrey V.

PY - 2015/7/20

Y1 - 2015/7/20

N2 - Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[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°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) 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 θ equal to 0.78 cm3 K mol-1 and -31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]- and [CrCp∗2]+[1]-, i.e., changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) 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 MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product. (Chemical Equation Presented).

AB - Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[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°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) 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 θ equal to 0.78 cm3 K mol-1 and -31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]- and [CrCp∗2]+[1]-, i.e., changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) 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 MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product. (Chemical Equation Presented).

UR - http://www.scopus.com/inward/record.url?scp=84937689839&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.5b01033

DO - 10.1021/acs.inorgchem.5b01033

M3 - Article

AN - SCOPUS:84937689839

VL - 54

SP - 7007

EP - 7013

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -