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Polymers 2017, 9(12), 644;

Four Mixed-Ligand Zn(II) Three-Dimensional Metal-Organic Frameworks: Synthesis, Structural Diversity, and Photoluminescent Property

Department of Chemistry, Soochow University, Taipei 11102, Taiwan
National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
Instrumentation Center, National Taiwan University, Taipei 10617, Taiwan
Authors to whom correspondence should be addressed.
Received: 29 October 2017 / Revised: 21 November 2017 / Accepted: 21 November 2017 / Published: 25 November 2017
(This article belongs to the Special Issue Coordination Polymer)
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Assemblies of four three-dimensional (3D) mixed-ligand coordination polymers (CPs) having formulas, {[Zn2(bdc)2(4-bpdh)]·C2H5OH·2H2O}n (1), [Zn(bdc)(4-bpdh)]n (2), {[Zn2(bdc)2(4-bpdh)2]·(4-bpdh)}n (3), and {[Zn(bdc)(4-bpdh)]·C2H5OH}n (4) (bdc2− = dianion of 1,4-benzenedicarboxylic acid, 4-bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) have been synthesized and structurally characterized by single-crystal X-ray diffraction method. Structural determination reveals that the coordination numbers (geometry) of Zn(II) ions in 1, 2, 3, and 4 are five (distorted square-pyramidal (SP)), six (distorted octahedral (Oh)), five (trigonal-bipyramidal (TBP)), and four (tetrahedral (Td)), respectively, and are bridged by 4-bpdh with bis-monodentate coordination mode and bdc2− ligands with bis-bidentate in 1, chelating/bidentate in 2, bis-monodentate and bis-bidentate in 3, and bis-monodentate in 4, to generate two-fold interpenetrating 3D cube-like metal-organic framework (MOF) with pcu topology, non-interpenetrating 3D MOF, two-fold interpenetrating 3D rectangular-box-like MOF with pcu topology and five-fold interpenetrating diamondoid-like MOF with dia topology, respectively. These different intriguing architectures indicate that the coordination numbers and geometries of Zn(II) ions, coordination modes of bdc2− ligand, and guest molecules play important roles in the construction of MOFs and the formation of the structural topologies and interpenetrations. Thermal stabilities, and photoluminescence study of 14 were also studied in detail. The complexes exhibit ligands based photoluminescence properties at room temperature. View Full-Text
Keywords: coordination polymer; metal-organic framework; structural topology; interpenetration; photoluminescence coordination polymer; metal-organic framework; structural topology; interpenetration; photoluminescence

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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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Wang, C.-C.; Ke, S.-Y.; Cheng, C.-W.; Wang, Y.-W.; Chiu, H.-S.; Ko, Y.-C.; Sun, N.-K.; Ho, M.-L.; Chang, C.-K.; Chuang, Y.-C.; Lee, G.-H. Four Mixed-Ligand Zn(II) Three-Dimensional Metal-Organic Frameworks: Synthesis, Structural Diversity, and Photoluminescent Property. Polymers 2017, 9, 644.

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