4.7 Article

Lanthanide Coordination Polymers Constructed from Imidazole-4,5-Dicarboxylate and Sulfate: Syntheses, Structural Diversity, and Photoluminescent Properties

Journal

CRYSTAL GROWTH & DESIGN
Volume 12, Issue 7, Pages 3675-3683

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/cg300476e

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Funding

  1. National Natural Science Foundation of China [21071099, 20831005]

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Three series of lanthanide coordination polymers of {[Ln(2)(HIDC)(2)(SO4)(H2O)(5)]center dot H2O}(n) (CPs-1Ln, Ln = Sm, Eu, Tb, Dy, Ho, Er, and Yb), {(H(2)prz)[Ln(2)(HIDC)(2)(SO4)(2)]} (CPs-2Ln, Ln = Sm and Eu), and [Ln(2)(HIDC)(2)(SO4)(H2O)(2)](n) (CPs-3Ln, Ln = Tb, Dy, Ho, Er, and Yb) have been hydrothermally synthesized by the reactions of Ln(NO3)(3)center dot 6H(2)O with imidazole-4,5-dicarboxylic acid (H3IDC) and sulfuric acid (H2SO4) in the presence of piperazine (prz) at different temperatures. The results of the single-crystal X-ray diffraction analysis reveal that CPs-1Ln presents a three-dimensional (3D) architecture, in which alternating one-dimensional (1D) right-/left-handed helical chains of [Ln(2)(HIDC)(2)](infinity) are interlinked by mu(3)-SO42- anions. CPs-2Ln assumes a H(2)prz(2+) templated 3D anionic layer-pillared metal-organic framework (MOF) of {[Ln(2)(HIDC)(2)(SO4)(2)]}(n)(2n-), in which two-dimensional (2D) (6,3) network layers of [Ln(2)(HIDC)(2)](n)(2n+) are pillared by mu(2)-SO42- anions. CPs-3Ln is a 2D layer structure, in which two 2D (6,3) monotayers of [Ln(2)(HIDC)(2)(H2O)(2)](n)(2n+) are connected by mu(2)-SO42- anions to form a 2D double-layer structure. The adjacent 2D double-layers are further stacked together via strong hydrogen bonding interactions to generate a 3D supramolecular framework. In addition, the results of photoluminescent measurements for Sm (1Sm and 2Sm), Eu (1Eu and 2Eu), Tb (1Tb and 3Tb), and Dy (1Dy and 3Dy) compounds in the solid state at room temperature indicate that different structural types have a different influence on their characteristic photoluminescences.

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