Issue 20, 2016

Lanthanide-based entangled coordination polymers connected by thiophene-2,5-dicarboxylate: solvothermal syntheses, crystal structures, luminescence and magnetic properties

Abstract

Nine novel coordination polymers (CPs) with the formulas [M6(TDA)9(DEF)5(H2O)3]n [M = Ce (1), Pr (2), Nd (3), Sm (4)], [Eu4(TDA)6(DEF)3(H2O)2]n (5), [Gd2(TDA)3(DEF)2]n·H2O (6), [Tb2(TDA)3(DEF)2]n·0.5H2O (7), [Dy2(TDA)3(DEF)2]n·H2O (8) and [Yb2(TDA)3(DEF)2]n·0.5H2O (9) (TDA = 2,5-thiophenedicarboxylate anion and DEF = diethylformamide) have been synthesized at different temperatures in a DEF–H2O solvent system under solvothermal conditions. All the compounds were characterized by single crystal X-ray diffraction analysis (XRD), Fourier transformation vibrational spectroscopy (FT-IR) and thermal analysis (TGA). Structural analyses of CPs 1–4 reveal that the polymers crystallize in the orthorhombic space group Pna21 and form 3D frameworks with large volumes 10 378.1(5), 10 230.5(5), 10 171.9(5) and 10 077.1(11) Å3, respectively. The M(III) ions of CPs 1–4 exhibit nine and eight coordination numbers with diverse geometries. Structural analyses of CPs 5 and 6–9 unveil that the polymers crystallize in the monoclinic system, with space groups P21 and P2/c, respectively, forming a 3D network. The TDA ligand exhibits two coordination modes [(κ11)–(κ11)-μ4 and (κ212)–(κ11)-μ5] which interconnect the metal ions to generate 3D novel metal–organic frameworks. The luminescence properties of 4, 5, 7 and 8, and the magnetic properties of 6–8 were investigated.

Graphical abstract: Lanthanide-based entangled coordination polymers connected by thiophene-2,5-dicarboxylate: solvothermal syntheses, crystal structures, luminescence and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
06 Feb 2016
Accepted
13 Apr 2016
First published
04 May 2016

CrystEngComm, 2016,18, 3617-3634

Lanthanide-based entangled coordination polymers connected by thiophene-2,5-dicarboxylate: solvothermal syntheses, crystal structures, luminescence and magnetic properties

M. Yawer, M. Kariem, P. Sood and H. N. Sheikh, CrystEngComm, 2016, 18, 3617 DOI: 10.1039/C6CE00321D

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