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Magnetochemistry 2018, 4(3), 38; https://doi.org/10.3390/magnetochemistry4030038

Heterobimetallic One-Dimensional Coordination Polymers MICuII (M = Li and K) Based on Ferromagnetically Coupled Di- and Tetracopper(II) Metallacyclophanes

1
Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Av. Antônio Carlos 6627, Pampulha, Belo Horizonte, Minas Gerais 31270901, Brazil
2
Centro Federal de Educação Tecnológica de Minas Gerais, Av. Amazonas 5855, Belo Horizonte, Minas Gerais 30421169, Brazil
3
Departamento de Química Inorgánica/Instituto de Ciencia Molecular (ICMol), Universitat de València, C/ Catedrático José Beltrán 2, 46980 Paterna (València), Spain
*
Author to whom correspondence should be addressed.
Received: 17 July 2018 / Revised: 16 August 2018 / Accepted: 16 August 2018 / Published: 25 August 2018
(This article belongs to the Special Issue Multifunctional Molecule-based Magnetic Materials)
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Abstract

The synthesis, crystal structure and magnetic properties of the coordination polymers of formula [EDAP{Li6(H2O)8[(Cu2(μ-mpba)2)2(H2O)2]}]n (1) and [(EDAP)2{K(H2O)4[Cu2(μ-mpba)2(H2O)2]}Cl·2H2O]n (2), in which mpba = N,N′-1,3-phenylenebis(oxamate) and EDAP2+ = 1,1′-ethylenebis(4-aminopyridinium) are described. Both compounds have in common the presence of the [Cu2(mpba)2]4− tetraanionic unit which is a [3,3] metallacyclophane motif in which the copper(II) ions are five-coordinate in a distorted square pyramidal surrounding. The complex anion in 1 is dimerized through double out-of-plane copper to outer carboxylate-oxygen atoms resulting in the centrosymmetric tetracopper(II) fragment [Cu4(μ-mpba)4(H2O)2]8− which act as a ligand toward six hydrated lithium(I) cations leading to anionic ladder-like double chains whose charge is neutralized by the EDAP2+ cations. In the case of 2, each dicopper(II) entity acts as a ligand towards tetraquapotassium(I) units to afford anionic zig zag single chains of formula {K(H2O)4[Cu2(μ-mpba)2(H2O)2]}n3n− plus EDAP2+ cations and non-coordinate chloride anions. Cryomagnetic measurements on polycrystalline samples 1 and 2 show the occurrence of ferromagnetic interactions between the copper(II) ions across the –Namidate–(C–C–C)phenyl–Namidate– exchange pathway [J = +10.6 (1) and +8.22 cm−1 (2)] and antiferromagnetic ones through the double out-of-plane carboxylate-oxygen atoms [j = −0.68 cm−1 (1), the spin Hamiltonian being defined as H = J ( S C u 1 · S C u 2 + S C u 2 i · S C u 1 i ) j ( S C u 2 · S C u 2 i ) ]. View Full-Text
Keywords: oxamate; copper(II); crystal engineering; spin polarization; ferromagnetic coupling; coordination polymers oxamate; copper(II); crystal engineering; spin polarization; ferromagnetic coupling; coordination polymers
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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T. da Cunha, T.; X. C. Oliveira, W.; F. Pedroso, E.; Lloret, F.; Julve, M.; L. M. Pereira, C. Heterobimetallic One-Dimensional Coordination Polymers MICuII (M = Li and K) Based on Ferromagnetically Coupled Di- and Tetracopper(II) Metallacyclophanes. Magnetochemistry 2018, 4, 38.

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