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Six novel coordination polymers based on the 5-(1H-tetrazol-5-yl)isophthalic acid ligand: structures, luminescence, and magnetic properties†
CrystEngComm ( IF 2.6 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1039/c8ce00030a
Xiu-Mei Zhang 1, 2, 3, 4, 5 , Feng Liu 1, 2, 3, 4 , Wei Gao 1, 2, 3, 4 , Hong Huang 1, 2, 3, 4 , Jie-Ping Liu 1, 2, 3, 4
Affiliation  

Six new coordination polymers (CPs), namely, [Mn2(OH)(TZI)(DMA)] (1), [Cu2(OH)(TZI)(DMA)]·3.5H2O (2), [Co2(OH)(TZI)(H2O)2] (3), [Zn2(OH)(TZI)(2,2′-bpy)]·H2O (4), [Zn2(OH)(TZI)(phen)]·2H2O (5) and [Zn2(OH)(TZI)(4,4′-bpy)0.5] (6), (H3TZI = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, and DMA = N,N-dimethylacetamide), have been synthesized under solvo-/hydrothermal conditions. Both 1 and 2 exhibit 3D structures containing butterfly-shaped tetranuclear M43-OH)2 clusters as secondary building units (SBUs). In 1, the SBUs are connected into 1D chains by the tetrazolate groups of the TZI ligands and the chains are further interlinked into a (4,8)-connected 3D net by the TZI spacers. In 2, the SBUs are directly connected by TZI to give a (3,6)-connected 3D framework. CP 3 features a double-layered structure based on corner-sharing Co33-OH) triangle Δ-chains in which Co(II) ions are bridged by mixed (μ4-tetrazolate)(μ3-OH)(μ2-COO) bridges. CPs 4–6 were synthesized by the reactions of the H3TZI ligands, Zn(NO3)2 and three different N-donor auxiliary ligands. The auxiliary ligands change from chelating ligands (2,2′-bpy, phen) to 4,4′-bpy, which leads to remarkable structural changes from 2D to 3D. CPs 4 and 5 display 2D structures with dinuclear motifs as SBUs. In 4, the dinuclear motifs with mixed double (μ2-tetrazolate)(μ2-OH) bridges are connected by the TZI spacers to produce a 2D framework. Differently, in 5, the dinuclear motifs with mixed double (μ2-COO)(μ2-OH) bridges are interlinked into a 2D framework with a (4,4)-connected net topology. In 6, the square Zn4O4 clusters are interlinked by the organic ligands into a 3D framework with a (4,10)-connected (44·62)(412·58·616·76·83) topology. Magnetic studies indicate that CPs 1–3 exhibit antiferromagnetic coupling. Further magnetic measurement demonstrates that CPs 1 and 3 show no magnetic ordering above 2 K. CPs 4–6 exhibit strong luminescence with different energies in the solid state at room temperature.

中文翻译:

基于5-(1 H-四唑-5-基)间苯二甲酸配体的六种新型配位聚合物:结构,发光和磁性

六种新的配位聚合物(CPs),即[Mn 2(OH)(TZI)(DMA)](1),[Cu 2(OH)(TZI)(DMA)]·3.5H 2 O(2),[ Co 2(OH)(TZI)(H 2 O)2 ](3),[Zn 2(OH)(TZI)(2,2'-bpy)]·H 2 O(4),[Zn 2(OH) )(TZI)(phen)]·2H 2 O(5)和[Zn 2(OH)(TZI)(4,4'-bpy)0.5 ](6),(H 3TZI = 5-(4-(四唑-5-基)苯基)间苯二甲酸,2,2'-bpy = 2,2'-联吡啶,phen = 1,10-菲咯啉,4,4'-bpy = 4,在溶剂-/水热条件下已经合成了4'-联吡啶,并且DMA = NN-二甲基乙酰胺。既12显示出含有蝴蝶形四核中号3D结构4(μ 3 -OH)2簇次级结构单元(的SBU)。在图1中,SBU通过TZI配体的四唑酸酯基团连接成一维链,并且这些链通过TZI间隔基进一步互连成(4,8)连接的3D网。在2,SBU通过TZI直接连接以提供(3,6)连接的3D框架。CP 3设有基于角共享一个双层结构共3(μ 3 -OH)三角形Δ链,其中的Co(II)离子被混合(μ桥接4 -tetrazolate)(μ 3 -OH)(μ 2 -COO)桥。CP 4–6是通过H 3 TZI配体,Zn(NO 32和三种不同的N供体辅助配体的反应合成的。辅助配体从螯合配体(2,2'-bpy,phen)变为4,4'-bpy,这导致了从2D到3D的显着结构变化。CP 4图5显示具有双核基序的2D结构作为SBU。在4,双核基序用混合双(μ 2 -tetrazolate)(μ 2 -OH)桥由TZI间隔物连接,以产生2D框架。不同地,在5,双核基序用混合双(μ 2 -COO)(μ 2 -OH)桥相通成具有(4,4)一个2D框架-连接网的拓扑结构。在6中,方形Zn 4 O 4簇通过有机配体相互连接成3D骨架,并具有(4,10)连接的(4 4 ·6 2)(4 12 ·5 8 ·6 16·7 6 ·8 3)拓扑。磁性研究表明,CP 1-3表现出反铁磁耦合。此外磁测量表明,CP的13示出上述2 K. CP的无磁有序4-6显示出在室温下以固体状态不同能量强发光。
更新日期:2018-02-22
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