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Issue 35, 2018
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A series of 3D lanthanide coordination polymers decorated with a rigid 3,5-pyridinedicarboxylic acid linker: syntheses, structural diversity, DFT study, Hirshfeld surface analysis, luminescence and magnetic properties

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Abstract

Single crystal X-ray diffraction studies reveal the formation of six new coordination polymers (CPs) with the general formulas [Dy(3,5-pdc)(3,5-pdcH)(H2O)2]n·nH2O (1), [Pr2(3,5-pdc)3(H2O)2]n·2n(H2O) (2), [Sm2(3,5-pdc)3(H2O)3]n·nH2O (3), {[Eu2(3,5-pdc)3(H2O)3(CH3CHO)]n·n[2(H2O)(DMF)]} (4), {[Gd2(3,5-pdc)3 (H2O)2]n·2nH2O} (5) and [Er(3,5-pdc)(adip)0.5(H2O)]n (6) (where 3,5-pdc2− = fully deprotonated; 3,5-pdcH = partially deprotonated 3,5-pyridinedicarboxylic acid; adip2− = fully deprotonated adipic acid; and DMF = dimethylformamide) by solvothermal self-assembly of lanthanide ions with rigid 3,5-pyridinedicarboxylic acid as a linker and adipic acid as an auxiliary flexible spacer (only coordinated in CP 6). CPs 1 and 2 crystallize in the triclinic P[1 with combining macron] space group, whereas CPs 3, 4 and 6 crystallize in the monoclinic P21/n, P21/c and C2/c space groups, respectively. CP 5 exhibits the trigonal R3 space group. The 3,5-pdc ligand exhibits eight diverse coordination modes in CPs 1–6, whereas the adipic acid spacer in CP 6 shows only one coordination mode (μ4–κO:κO,O:κO:κO,O). The organic ligands interconnect with metal ions to generate 3D metal–organic frameworks with a variety of intriguing topologies. Theoretical studies, DFT calculations and Hirshfeld surface analysis support the structures adopted by the various CPs. CPs 3 (Sm) and 4 (Eu) emit strong ligand-sensitized characteristic ff luminescence. Weak ferromagnetic interactions have been studied at low temperatures for CP 1 and CP 5.

Graphical abstract: A series of 3D lanthanide coordination polymers decorated with a rigid 3,5-pyridinedicarboxylic acid linker: syntheses, structural diversity, DFT study, Hirshfeld surface analysis, luminescence and magnetic properties

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Publication details

The article was received on 13 Jun 2018, accepted on 05 Aug 2018 and first published on 16 Aug 2018


Article type: Paper
DOI: 10.1039/C8DT02429D
Citation: Dalton Trans., 2018,47, 12318-12336
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    A series of 3D lanthanide coordination polymers decorated with a rigid 3,5-pyridinedicarboxylic acid linker: syntheses, structural diversity, DFT study, Hirshfeld surface analysis, luminescence and magnetic properties

    M. Kumar, M. Kariem, H. N. Sheikh, A. Frontera, S. K. Seth and A. K. Jassal, Dalton Trans., 2018, 47, 12318
    DOI: 10.1039/C8DT02429D

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