Research output: Contribution to journal › Article › peer-review
Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives. / Sherstobitova, Tatiana; Maryunina, Kseniya; Tolstikov, Svyatoslav et al.
In: ACS Omega, Vol. 4, No. 17, 22.10.2019, p. 17160-17170.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
AU - Sherstobitova, Tatiana
AU - Maryunina, Kseniya
AU - Tolstikov, Svyatoslav
AU - Letyagin, Gleb
AU - Romanenko, Galina
AU - Nishihara, Sadafumi
AU - Inoue, Katsuya
N1 - Publisher Copyright: Copyright © 2019 American Chemical Society. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/10/22
Y1 - 2019/10/22
N2 - Reaction of Cu(hfac)2 with methyl- and bromo-3-pyridyl-substituted nitronyl nitroxides (LR) leads to assemble a diverse set of coordination complexes: mononuclear [Cu(hfac)2L2-Me], binuclear [{Cu(hfac)2}2(H2O)L2-Me], trinuclear [{Cu(hfac)2}3(L6-Br)2], pentanuclear [{Cu(hfac)2}5(L2-Me)2], and [{Cu(hfac)2}5(L2-Me)4], cocrystals [Cu(hfac)2(L2-Br)2]·[Cu(hfac)2(H2O)2] and [Cu(hfac)2(L2-Br)2]·2[Cu(hfac)2H2O], one-dimensional polymers [Cu(hfac)2L2-Br]n and [Cu(hfac)2L6-Br]n, and cyclic dimers [Cu(hfac)2L5-Me]2, [Cu(hfac)2L5-Br]2, and [Cu(hfac)2L6-Me]2. The molecular structures of the obtained complexes are strongly affected by the substituent type and its location in the pyridine heterocycle. Occupation of the second position of the pyridine ring increases the steric hindrance of both imine and nitroxide coordination sites of L2-R, which is favorable for the formation of various conformers and precipitation of complexes with different molecular structures. The pentanuclear [{Cu(hfac)2}5(L2-Me)2] and [{Cu(hfac)2}5(L2-Me)4] complexes do not have prior analogues and are valuable model objects for investigation of the mechanism of formation of various coordination polymers. The arrangement of long Cu-ONO bonds in {CuO6} square bipyramids due to the weakening nitroxide donor site in complexes, based on L2-Me, L2-Br, and L6-Br ligands, results in ferromagnetic exchange interactions between spins of Cu2+ ions and nitroxides. Complexes with substituents that do not considerably affect the coordination ability of ligands (L5-Me, L5-Br, and L6-Me) exhibit strong antiferromagnetic exchange interactions between spins of Cu2+ ions and nitroxides.
AB - Reaction of Cu(hfac)2 with methyl- and bromo-3-pyridyl-substituted nitronyl nitroxides (LR) leads to assemble a diverse set of coordination complexes: mononuclear [Cu(hfac)2L2-Me], binuclear [{Cu(hfac)2}2(H2O)L2-Me], trinuclear [{Cu(hfac)2}3(L6-Br)2], pentanuclear [{Cu(hfac)2}5(L2-Me)2], and [{Cu(hfac)2}5(L2-Me)4], cocrystals [Cu(hfac)2(L2-Br)2]·[Cu(hfac)2(H2O)2] and [Cu(hfac)2(L2-Br)2]·2[Cu(hfac)2H2O], one-dimensional polymers [Cu(hfac)2L2-Br]n and [Cu(hfac)2L6-Br]n, and cyclic dimers [Cu(hfac)2L5-Me]2, [Cu(hfac)2L5-Br]2, and [Cu(hfac)2L6-Me]2. The molecular structures of the obtained complexes are strongly affected by the substituent type and its location in the pyridine heterocycle. Occupation of the second position of the pyridine ring increases the steric hindrance of both imine and nitroxide coordination sites of L2-R, which is favorable for the formation of various conformers and precipitation of complexes with different molecular structures. The pentanuclear [{Cu(hfac)2}5(L2-Me)2] and [{Cu(hfac)2}5(L2-Me)4] complexes do not have prior analogues and are valuable model objects for investigation of the mechanism of formation of various coordination polymers. The arrangement of long Cu-ONO bonds in {CuO6} square bipyramids due to the weakening nitroxide donor site in complexes, based on L2-Me, L2-Br, and L6-Br ligands, results in ferromagnetic exchange interactions between spins of Cu2+ ions and nitroxides. Complexes with substituents that do not considerably affect the coordination ability of ligands (L5-Me, L5-Br, and L6-Me) exhibit strong antiferromagnetic exchange interactions between spins of Cu2+ ions and nitroxides.
KW - SPIN-TRANSITION
KW - FREE-RADICALS
KW - CRYSTAL
KW - COORDINATION
KW - CU(HFAC)(2)
KW - DESIGN
UR - http://www.scopus.com/inward/record.url?scp=85073161667&partnerID=8YFLogxK
U2 - 10.1021/acsomega.9b01575
DO - 10.1021/acsomega.9b01575
M3 - Article
C2 - 31656889
AN - SCOPUS:85073161667
VL - 4
SP - 17160
EP - 17170
JO - ACS Omega
JF - ACS Omega
SN - 2470-1343
IS - 17
ER -
ID: 21861578