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Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives

[Image: see text] Reaction of Cu(hfac)(2) with methyl- and bromo-3-pyridyl-substituted nitronyl nitroxides (L(R)) leads to assemble a diverse set of coordination complexes: mononuclear [Cu(hfac)(2)L(2-Me)], binuclear [{Cu(hfac)(2)}(2)(H(2)O)L(2-Me)], trinuclear [{Cu(hfac)(2)}(3)(L(6-Br))(2)], pentan...

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Autores principales: Sherstobitova, Tatiana, Maryunina, Kseniya, Tolstikov, Svyatoslav, Letyagin, Gleb, Romanenko, Galina, Nishihara, Sadafumi, Inoue, Katsuya
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6811855/
https://www.ncbi.nlm.nih.gov/pubmed/31656889
http://dx.doi.org/10.1021/acsomega.9b01575
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author Sherstobitova, Tatiana
Maryunina, Kseniya
Tolstikov, Svyatoslav
Letyagin, Gleb
Romanenko, Galina
Nishihara, Sadafumi
Inoue, Katsuya
author_facet Sherstobitova, Tatiana
Maryunina, Kseniya
Tolstikov, Svyatoslav
Letyagin, Gleb
Romanenko, Galina
Nishihara, Sadafumi
Inoue, Katsuya
author_sort Sherstobitova, Tatiana
collection PubMed
description [Image: see text] Reaction of Cu(hfac)(2) with methyl- and bromo-3-pyridyl-substituted nitronyl nitroxides (L(R)) leads to assemble a diverse set of coordination complexes: mononuclear [Cu(hfac)(2)L(2-Me)], binuclear [{Cu(hfac)(2)}(2)(H(2)O)L(2-Me)], trinuclear [{Cu(hfac)(2)}(3)(L(6-Br))(2)], pentanuclear [{Cu(hfac)(2)}(5)(L(2-Me))(2)], and [{Cu(hfac)(2)}(5)(L(2-Me))(4)], cocrystals [Cu(hfac)(2)(L(2-Br))(2)]·[Cu(hfac)(2)(H(2)O)(2)] and [Cu(hfac)(2)(L(2-Br))(2)]·2[Cu(hfac)(2)H(2)O], one-dimensional polymers [Cu(hfac)(2)L(2-Br)](n) and [Cu(hfac)(2)L(6-Br)](n), and cyclic dimers [Cu(hfac)(2)L(5-Me)](2), [Cu(hfac)(2)L(5-Br)](2), and [Cu(hfac)(2)L(6-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 L(2-R), which is favorable for the formation of various conformers and precipitation of complexes with different molecular structures. The pentanuclear [{Cu(hfac)(2)}(5)(L(2-Me))(2)] and [{Cu(hfac)(2)}(5)(L(2-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–O(NO) bonds in {CuO(6)} square bipyramids due to the weakening nitroxide donor site in complexes, based on L(2-Me), L(2-Br), and L(6-Br) ligands, results in ferromagnetic exchange interactions between spins of Cu(2+) ions and nitroxides. Complexes with substituents that do not considerably affect the coordination ability of ligands (L(5-Me), L(5-Br), and L(6-Me)) exhibit strong antiferromagnetic exchange interactions between spins of Cu(2+) ions and nitroxides.
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spelling pubmed-68118552019-10-25 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 Letyagin, Gleb Romanenko, Galina Nishihara, Sadafumi Inoue, Katsuya ACS Omega [Image: see text] Reaction of Cu(hfac)(2) with methyl- and bromo-3-pyridyl-substituted nitronyl nitroxides (L(R)) leads to assemble a diverse set of coordination complexes: mononuclear [Cu(hfac)(2)L(2-Me)], binuclear [{Cu(hfac)(2)}(2)(H(2)O)L(2-Me)], trinuclear [{Cu(hfac)(2)}(3)(L(6-Br))(2)], pentanuclear [{Cu(hfac)(2)}(5)(L(2-Me))(2)], and [{Cu(hfac)(2)}(5)(L(2-Me))(4)], cocrystals [Cu(hfac)(2)(L(2-Br))(2)]·[Cu(hfac)(2)(H(2)O)(2)] and [Cu(hfac)(2)(L(2-Br))(2)]·2[Cu(hfac)(2)H(2)O], one-dimensional polymers [Cu(hfac)(2)L(2-Br)](n) and [Cu(hfac)(2)L(6-Br)](n), and cyclic dimers [Cu(hfac)(2)L(5-Me)](2), [Cu(hfac)(2)L(5-Br)](2), and [Cu(hfac)(2)L(6-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 L(2-R), which is favorable for the formation of various conformers and precipitation of complexes with different molecular structures. The pentanuclear [{Cu(hfac)(2)}(5)(L(2-Me))(2)] and [{Cu(hfac)(2)}(5)(L(2-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–O(NO) bonds in {CuO(6)} square bipyramids due to the weakening nitroxide donor site in complexes, based on L(2-Me), L(2-Br), and L(6-Br) ligands, results in ferromagnetic exchange interactions between spins of Cu(2+) ions and nitroxides. Complexes with substituents that do not considerably affect the coordination ability of ligands (L(5-Me), L(5-Br), and L(6-Me)) exhibit strong antiferromagnetic exchange interactions between spins of Cu(2+) ions and nitroxides. American Chemical Society 2019-10-07 /pmc/articles/PMC6811855/ /pubmed/31656889 http://dx.doi.org/10.1021/acsomega.9b01575 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Sherstobitova, Tatiana
Maryunina, Kseniya
Tolstikov, Svyatoslav
Letyagin, Gleb
Romanenko, Galina
Nishihara, Sadafumi
Inoue, Katsuya
Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title_full Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title_fullStr Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title_full_unstemmed Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title_short Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives
title_sort ligand structure effects on molecular assembly and magnetic properties of copper(ii) complexes with 3-pyridyl-substituted nitronyl nitroxide derivatives
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6811855/
https://www.ncbi.nlm.nih.gov/pubmed/31656889
http://dx.doi.org/10.1021/acsomega.9b01575
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