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Polymers 2018, 10(3), 229; https://doi.org/10.3390/polym10030229

Two New Three-Dimensional Pillared-Layer Co(II) and Cu(II) Frameworks Involving a [M2(EO-N3)2] Motif from a Semi-Flexible N-Donor Ligand, 5,5′-Bipyrimidin: Syntheses, Structures and Magnetic Properties

1
Department of Chemistry, Tunghai University, Taichung 407, Taiwan
2
Instrumentation Center, National Taiwan University, Taipei 106, Taiwan
*
Author to whom correspondence should be addressed.
Received: 30 January 2018 / Revised: 15 February 2018 / Accepted: 23 February 2018 / Published: 26 February 2018
(This article belongs to the Special Issue Coordination Polymer)
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Abstract

Two new three-dimensional (3D) Co(II)- and Cu(II)-azido frameworks, [Co2(N3)4(bpym)2]n (1) and [Cu2(N3)4(bpym)]n (2), were successfully synthesized by introducing a semi-flexible N-donor ligand, 5,5′-bipyrimidin (bpym), with different bridging modes and orientations. Compounds 1 and 2 were structurally characterized by X-ray crystallography, IR spectroscopy, thermogravimetry and elemental analysis. Compounds 1 and 2 are 3D pillared-layer frameworks with double end-on (EO) azido bridged dinuclear motifs, [M2(EO-N3)2]. In Compound 1, the bpym ligands show trans μ2-bridging mode and the role as pillars to connect the Co(II)-azido layers, composed of [Co2(EO-N3)2] motifs and single end-to-end (EE) azido bridges, to a 3D network with BN topology. In contrast, in 2, the bpym ligand adopts a twisted μ4-bridging mode, which not only connects the adjacent [Cu2(EO-N3)2] units to a layer, but also functions as a pillar for the layers of the 3D structure. The structural diversities between the two types of architectures can be attributed to the coordination geometry preference of the metal ions (octahedral for Co2+ and square pyramidal for Cu2+). Magnetic investigations revealed that Compound 1 exhibits ferromagnetic-like magnetic ordering due to spin canting with a critical temperature, TC = 33.0 K, and furthers the field-induced magnetic transitions of metamagnetism at temperatures below TC. Compound 2 shows an antiferromagnetic ordering with TN = 3.05 K and a field-induced magnetic transition of spin-flop at temperatures below the TN. View Full-Text
Keywords: semi-flexible N-donor ligand; coordination polymer; magnetic properties; spin canting; metamagnetism; spin-flop semi-flexible N-donor ligand; coordination polymer; magnetic properties; spin canting; metamagnetism; spin-flop
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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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Zhang, Z.-Z.; Chang, H.-T.; Kuo, Y.L.; Lee, G.-H.; Yang, C.-I. Two New Three-Dimensional Pillared-Layer Co(II) and Cu(II) Frameworks Involving a [M2(EO-N3)2] Motif from a Semi-Flexible N-Donor Ligand, 5,5′-Bipyrimidin: Syntheses, Structures and Magnetic Properties. Polymers 2018, 10, 229.

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