TY - JOUR
T1 - Heterospin π-heterocyclic radical-anion salt
T2 - Synthesis, structure, and magnetic properties of decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c ][1,2,5]thiadiazolidyl
AU - Semenov, Nikolay A.
AU - Pushkarevsky, Nikolay A.
AU - Lonchakov, Anton V.
AU - Bogomyakov, Artem S.
AU - Pritchina, Elena A.
AU - Suturina, Elizaveta A.
AU - Gritsan, Nina P.
AU - Konchenko, Sergey N.
AU - Mews, Ruediger
AU - Ovcharenko, Victor I.
AU - Zibarev, Andrey V.
PY - 2010/8/16
Y1 - 2010/8/16
N2 - Decamethylchromocene, CrII(η5-C 5(CH3)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 [2]+, 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]- (J1 = -40 ± 9 cm-1) and [2]+⋯ [2]+ (J2 = -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 J2 value is also in agreement with that calculated using the BS DFT approach (-0.33 cm-1).
AB - Decamethylchromocene, CrII(η5-C 5(CH3)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 [2]+, 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]- (J1 = -40 ± 9 cm-1) and [2]+⋯ [2]+ (J2 = -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 J2 value is also in agreement with that calculated using the BS DFT approach (-0.33 cm-1).
UR - http://www.scopus.com/inward/record.url?scp=77955483651&partnerID=8YFLogxK
U2 - 10.1021/ic101064c
DO - 10.1021/ic101064c
M3 - Article
AN - SCOPUS:77955483651
SN - 0020-1669
VL - 49
SP - 7558
EP - 7564
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -