Research output: Contribution to journal › Article › peer-review
Heterospin molecular complexes of Cu(hfac)2 with pyridyl-substituted nitronyl nitroxides: peculiarities of structure and magnetic properties. / Tolstikov, Svyatoslav E.; Kolesnikov, Andrey E.; Smirnova, Kristina A. et al.
In: New Journal of Chemistry, 10.04.2025.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Heterospin molecular complexes of Cu(hfac)2 with pyridyl-substituted nitronyl nitroxides: peculiarities of structure and magnetic properties
AU - Tolstikov, Svyatoslav E.
AU - Kolesnikov, Andrey E.
AU - Smirnova, Kristina A.
AU - Letyagin, Gleb A.
AU - Bogomyakov, Artem S.
AU - Romanenko, Galina V.
AU - Ovcharenko, Victor I.
N1 - The research was financially supported by the Russian Science Foundation (grant no. 23-13-00014).
PY - 2025/4/10
Y1 - 2025/4/10
N2 - A series of binuclear and tetranuclear Cu(hfac)2 complexes with pyridyl-substituted nitroxide radicals LR, where LR is 2-(4-R-pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (R = Cl, Br, CF3, OMe, OEt, i-Pr, n-Pr, Ph, cyclopentyl (CP), cyclohexyl (Cy), thiophen-2-yl (Thio)), were synthesized. The crystal structures of these complexes are formed by centrosymmetric molecules with the bridging paramagnetic ligand LR, connecting two Cu(hfac)2 units. In the tetranuclear complexes, the other two ONO atoms that are not involved in the formation of the binuclear unit are bound to additional Cu(hfac)2 or Cu(hfac)LR fragments. It was found that only for complexes with LThio and LPh, changing the temperature induces structural transformations in the environment of Cu atoms in the binuclear units. This is reflected in the anomalous behavior of the effective magnetic moment μeff with temperature. Magneto-structural correlations were established linking the rigidity of a pyridine fragment substituent with the possibility of a spin transition.
AB - A series of binuclear and tetranuclear Cu(hfac)2 complexes with pyridyl-substituted nitroxide radicals LR, where LR is 2-(4-R-pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (R = Cl, Br, CF3, OMe, OEt, i-Pr, n-Pr, Ph, cyclopentyl (CP), cyclohexyl (Cy), thiophen-2-yl (Thio)), were synthesized. The crystal structures of these complexes are formed by centrosymmetric molecules with the bridging paramagnetic ligand LR, connecting two Cu(hfac)2 units. In the tetranuclear complexes, the other two ONO atoms that are not involved in the formation of the binuclear unit are bound to additional Cu(hfac)2 or Cu(hfac)LR fragments. It was found that only for complexes with LThio and LPh, changing the temperature induces structural transformations in the environment of Cu atoms in the binuclear units. This is reflected in the anomalous behavior of the effective magnetic moment μeff with temperature. Magneto-structural correlations were established linking the rigidity of a pyridine fragment substituent with the possibility of a spin transition.
UR - https://www.mendeley.com/catalogue/99dfcc8b-8da0-341c-a974-a09e5e4b9657/
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-105003141786&origin=inward&txGid=f44b7ad3b95182e89db29c5ca6cdd9e0
U2 - 10.1039/d5nj00967g
DO - 10.1039/d5nj00967g
M3 - Article
JO - New Journal of Chemistry
JF - New Journal of Chemistry
SN - 1144-0546
ER -
ID: 65405009