TY - JOUR

T1 - A black-box approach to the construction of metal-radical multispin systems and analysis of their magnetic properties

AU - Kadilenko, E. M.

AU - Gritsan, N. P.

AU - Tretyakov, E. V.

AU - Fokin, S. V.

AU - Romanenko, G. V.

AU - Bogomyakov, A. S.

AU - Gorbunov, D. E.

AU - Schollmeyer, D.

AU - Baumgarten, M.

AU - Ovcharenko, V. I.

N1 - Funding Information: E. V. T. thanks German Academic Exchange Service DAAD (program “Bilateral Exchange of Academics”, 2015/ 50015739). S. V. F. and G. V. R. are grateful to the Russian Science Foundation (project 17-13-01022) for financial support of parts of this work: synthesis and XRD analyses of [Mn(hfac)2(DR)(H2O)]2 and [Mn(hfac)2(DR)]·CH2Cl2. E. M. K., D. E. G., and N. P. G. acknowledge the Russian Science Foundation (project 16-13-10155) for a financial support of the computational part of this work and the Supercomputer Centre of Novosibirsk State University for computational resources. Publisher Copyright: © The Royal Society of Chemistry. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/12/14

Y1 - 2020/12/14

N2 - An interaction of M(hfac)2 (M = Mn or Ni) with N-(bis(4,4,5,5-tetramethyl-3-oxido-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)methylene)-2-methyl-propan-2-amine oxide (a nitronyl nitroxide diradical with the >CN(O)-tert-Bu coupler) was investigated under various conditions. It was found that prolongation of reaction time caused transformation of the initial diradical into new diradicals with the unique >CN-OH coupling unit and formation of binuclear Mn(ii) and Ni(ii) complexes, which were characterized by X-ray diffraction analysis. The resulting binuclear heterospin complexes have a complicated magnetic structure with six paramagnetic centers and a number of exchange interaction channels between them, as well as between neighboring complexes. To adequately describe the magnetic properties of these complexes, high-level ab initio calculations of their electronic structure and parameters of the spin-Hamiltonian were carried out. The accuracy of the conventional broken-symmetry density functional theory approach in the calculation of the exchange interaction parameters was also verified

AB - An interaction of M(hfac)2 (M = Mn or Ni) with N-(bis(4,4,5,5-tetramethyl-3-oxido-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)methylene)-2-methyl-propan-2-amine oxide (a nitronyl nitroxide diradical with the >CN(O)-tert-Bu coupler) was investigated under various conditions. It was found that prolongation of reaction time caused transformation of the initial diradical into new diradicals with the unique >CN-OH coupling unit and formation of binuclear Mn(ii) and Ni(ii) complexes, which were characterized by X-ray diffraction analysis. The resulting binuclear heterospin complexes have a complicated magnetic structure with six paramagnetic centers and a number of exchange interaction channels between them, as well as between neighboring complexes. To adequately describe the magnetic properties of these complexes, high-level ab initio calculations of their electronic structure and parameters of the spin-Hamiltonian were carried out. The accuracy of the conventional broken-symmetry density functional theory approach in the calculation of the exchange interaction parameters was also verified

UR - http://www.scopus.com/inward/record.url?scp=85097583789&partnerID=8YFLogxK

U2 - 10.1039/d0dt03184d

DO - 10.1039/d0dt03184d

M3 - Article

C2 - 33188374

AN - SCOPUS:85097583789

VL - 49

SP - 16916

EP - 16927

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 46

ER -