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Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers

Abstract : I 2 (4,4'-bipy)]·4.5H 2 O 2 obtained under solvothermal synthesis using 1H-imidazole-4,5-dicarboxylic acid (H 3 IDC) as principal N,O-bifunctional organic linker. In both compounds, the stabilization of the Cu I cations is achieved only by the coordination of N-atoms belonging to the organic ligands. While, 1 presents a 2D honeycomb network obtained by the coordination of single organic linker (IDC 3-), 2 contains three different organic ligands (IDC 3-, C 2 O 4 2-and 4,4'-bipy), which allow the construction of a 3D network. From a magnetic point of view, 1 and 2 behave as simple paramagnets at high temperature, presenting ferromagnetic interactions below 50 K, a positive magnetic coupling constant of J = 0.60 cm-1 and J = 0.22 cm-1 was obtained for 1 and 2 respectively. To the best our knowledge 1 and 2 correspond to the second and third reported examples containing a Cu I /Cu II mixed valence system assembled with Gd III cations, thus enriching the chemistry involved in the 3d-4f metal-organic materials.
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Carlos Cruz, Francisco Rubio, Diego Venegas-Yazigi, Nathalie Audebrand, Christophe Calers, et al.. Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers. Crystal Growth and Design, American Chemical Society, 2019, 19 (12), pp.7055-7066. ⟨10.1021/acs.cgd.9b00816⟩. ⟨hal-02438533⟩

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