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