Abstract

Two new three-dimensional 3d–4f heterometallic coordination polymers, {[Tb2(DMSO)6][LCu]3·5CH3OH}n1 and {[Er2(DMSO)4][LCu]3·2DMSO·6CH3OH}n2 (DMSO = dimethyl sulfoxide), based on carboxyl-containing metalloligand LCu ([Cu(2,4-pydca)2]2−, 2,4-pydca = pyridine-2,4-dicarboxylate) and lanthanide ions (TbIII, ErIII), have been synthesized with inter-diffusion method and well characterized. Single-crystal X-ray diffraction studies indicates that 1 and 2 crystallize in the space group of P − 1 of the triclinic crystal system and show 3D frameworks, which are severally established by {Tb2} and {Er2} clusters bridging with LCu metalloligands. The whole frameworks of 1 and 2 illustrate the similar 6-connected single-nodal topology with the point symbol of {412·63}. The most structural difference between two coordination polymers is that 2 exhibits a twofold interpenetrated framework. Thermal analysis reveals that 1 and 2 have similar thermal behavior with the skeleton both collapse after 292 °C. Magnetic measurements suggest that 1 and 2 exhibit the weak antiferromagnetic properties, which may be due to the existence of crystal-field effects of LnIII ions and the contribution of orbital couplings between the spin centers.

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