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

机译:四种混合配体的Zn(II)三维金属-有机骨架:合成,结构多样性和光致发光性能

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摘要

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.
机译:四个具有{{Zn2(bdc)2(4-bpdh)]·C2H5OH·2H2O} n( 1 )式的三维(3D)混合配体配位聚合物(CP)的组合, [Zn(bdc)(4-bpdh)] n( 2 ),{[Zn2(bdc)2(4-bpdh)2]·(4-bpdh)} n( 3 )和{[Zn(bdc)(4-bpdh)]·C2H5OH} n( 4 )(bdc 2 − =二价阴离子为1,4合成了4-bpdh = 2,5-双(4-吡啶基)-3,4-二氮杂2,4-己二烯的-苯二甲酸,并通过单晶X射线衍射法对其结构进行了表征。结构确定表明 1 2 3 4 <>中Zn(II)离子的配位数(几何形状) / strong>分别是5个(扭曲的方形锥体(SP)),6个(扭曲的八面体(Oh)),5个(三角形-双锥体(TBP))和4个(四面体(Td)),并由4桥接-bpdh具有双单齿配位模式和bdc 2-配体,双配位在 1 中,螯合/双配位在 2 中,双配位并在 3 中使用bis-bidentate,在 4 中使用bis-monodentate,以生成具有 pcu的互穿互穿的3D立方体状金属有机框架(MOF) 拓扑,非互穿3D MOF,具有 pcu 拓扑的两重互穿3D矩形盒状MOF和具有 dia 拓扑。这些不同的有趣结构表明,Zn(II)离子的配位数和几何形状,bdc 2-配体的配位模式以及客体分子在MOF的构建和结构的形成中起重要作用。拓扑和互穿。还详细研究了 1 4 的热稳定性和光致发光研究。所述复合物在室温下显示出基于配体的光致发光性质。

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