基于一维双螺旋链的锌配合物的合成与荧光性能

doi:10.11944/j.issn.1000-0518.2018.11.170464

摘要/Abstract

摘要：

选择配体N,N'-双(3-吡啶)丙二酰胺(3-bpma)、1,4-对苯二乙酸(H₂pda)和硝酸锌在水热条件下,自组装制备了一个基于双螺旋链的三维超分子锌配合物[Zn(3-bpma)(pda)]_n(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射分析进行了晶体结构表征。单晶结构分析表明标题锌配合物是正交晶系,Pna21空间群,晶胞参数a=1.62512(11) nm,b=1.15947(8) nm,c=1.19282(8) nm,α=90°,β=90°,γ=90°,V=2.2476(3) nm³,M_r=513.80,D_c=1.518 g/cm³,Z=4,F(000)=1056,R₁=0.0381,wR₂=0.0669。金属锌离子被两种桥连配体3-bpma和pda连接形成一种一维双螺旋链状结构,相邻的链间进一步通过氢键作用拓展成为三维超分子网络结构。标题锌配合物具有强荧光发射特性,而且其对不同的有机溶剂分子和金属离子有显著的荧光传感特性,可以作为检测硝基苯的高灵敏性荧光传感材料。 CCDC:1811967

关键词: 水热合成, 锌配合物, 螺旋结构, 荧光性质, 荧光传感

Abstract:

A zinc complex based on the one-dimensional(1D) double-helical chains was hydrothermally self-assembled by selecting the organic ligand N,N'-bis(3-pyridyl)malonamide (3-bpma), 1,4-phenylenediacetic acid(H₂pda) and zinc nitrate, [Zn(3-bpma)(pda)]_n(1), then structurally characterized by infrared spectroscopy(IR), element analysis, thermogravimetry(TG) and X-ray single-crystal diffraction. The single-crystal structural analysis reveals that this zinc complex is an orthorhombic system with space group Pna21, its cell parameters are:a=1.62512(11) nm, b=1.15947(8) nm, c=1.19282(8) nm, α=90°, β=90°, γ=90°, V=2.2476(3) nm³, M_r=513.80, D_c=1.518 g/cm³, Z=4, F(000)=1056, R₁=0.0381, wR₂=0.0669. The zinc ions are bridged by two kinds of ligands 3-bpma and pda to form a 1D double-helical chain, then the adjacent chains are extended into the 3D supramolecular network through the hydrogen bonding interactions. The title zinc complex shows a strong fluorescence emission characteristic. Moreover, this complex possesses remarkable fluorescent sensing behaviors for organic solvent molecules and metal ions, which may be a potential fluorescent sensing material for detecting nitrobenzene. CCDC:1811967.

Key words: hydrothermal synthesis, zinc complex, helical structure, fluorescent property, fluorescent sensing

林宏艳,田原,王青林,曾凌,刘国成,赵延玉. 基于一维双螺旋链的锌配合物的合成与荧光性能[J]. 应用化学, 2018, 35(11): 1372-1377.

LIN Hongyan,TIAN Yuan,WANG Qinglin,ZENG Ling,LIU Guocheng,ZHAO Yanyu. Synthesis and Fluorescence Properties of a Zinc Complex Based on the One-Dimensional Double-Helical Chains[J]. Chinese Journal of Applied Chemistry, 2018, 35(11): 1372-1377.

参考文献

[1]	Li J R,Sculley J,Zhou H C.Metal-Organic Frameworks for Separations[J]. Chem Rev,2012,112(2):869-932.
[2]	Hu Z C,Deibert B J,Li J.Luminescent Metal-Organic Frameworks for Chemical Sensing and Explosive Detection[J]. Chem Soc Rev,2014,43(16):5815-5840.
[3]	Zhao S S,Yang J,Liu Y Y,et al. Fluorescent Aromatic Tag-Functionalized MOFs for Highly Selective Sensing of Metal Ions and Small Organic Molecules[J]. Inorg Chem,2016,55(5):2261-2273.
[4]	Lin R B,Li F,Liu S Y,et al. A Noble-Metal-Free Porous Coordination Framework with Exceptional Sensing Efficiency for Oxygen[J]. Angew Chem Int Ed,2013,52(50):13429-13433.
[5]	Haldar R,Matsuda R,Kitagawa S,et al. Amine-Responsive Adaptable Nanospaces:Fluorescent Porous Coordination Polymer for Molecular Recognition[J]. Angew Chem Int Ed,2014,53(44):11772-11777.
[6]	Liu Z Q,Zhao Y,Wang P,et al. Metal-Organic Frameworks with 1,4-Di(1H-imidazol-4-yl)benzene and Varied Carboxylate Ligands for Selectively Sensing Fe(Ⅲ) Ions and Ketone Molecules[J]. Dalton Trans,2017,46(40):13943-13951.
[7]	Douvali A,Tsipis A C,Eliseeva S V,et al. Turn-On Luminescence Sensing and Real-Time Detection of Traces of Water in Organic Solvents by a Flexible Metal-Organic Framework[J]. Angew Chem Int Ed,2015,54(5):1651-1656.
[8]	Wang H,Yang W T,Sun Z M.Mixed-Ligand Zn-MOFs for Highly Luminescent Sensing of Nitro Compounds[J]. Chem Asian J,2013,8(5):982-989.
[9]	Yi F Y,Wang Y,Li J P,et al. An Ultrastable Porous Metal-Organic Framework Luminescent Switch Towards Aromatic Compounds[J]. Mater Horiz,2015,2(2):245-251.
[10]	Lin H Y,Sun J J,Liu G C,et al. Self-assembly, Structures and Properties of Three New Ni(Ⅱ) Coordination Polymers Derived from Two Different Bis-pyridyl-Bis-amide Ligands and Two Aromatic Polycarboxylates[J]. J Chem Sci,2017,129(1):9-20.
[11]	Lin H Y,Rong X,Liu G C,et al. Fluorescent Sensing and Electrocatalytic Properties of Three Zn(Ⅱ)/Co(Ⅱ) Coordination Complexes Containing Two Different Dicarboxylates and Two Various Bis(pyridyl)-Bis(amide) Ligands[J]. J Mol Struct,2016,1119:396-403.
[12]	Wang X L,Luan J,Lin H Y,et al. Metal(Ⅱ)-Organic Coordination Polymers Modulated by Two Isomeric Semirigid Bis-pyridyl-Bis-amide Ligands:Structures, Fluorescent Sensing Behavior, and Selective Photocatalysis[J]. ChemPlusChem,2014,79(12):1691-1702.
[13]	Lin H Y,Lu H Z,Le M,et al. Effect of Three Bis-pyridyl-Bis-amide Ligands with Various Spacers on the Structural Diversity of New Multifunctional Cobalt(Ⅱ) Coordination Polymers[J]. J Solid State Chem,2015,226:66-73.
[14]	Cheng P C,Kuo P T,Liao Y H,et al. Ligand-Isomerism Controlled Structural Diversity of Zn(Ⅱ) and Cd(Ⅱ) Coordination Polymers from Mixed Dipyridyladipoamide and Benzenedicarboxylate Ligands[J]. Cryst Growth Des,2013,13(2):623-632.
[15]	Chen Y Q,Liu S J,Li Y W,et al. Mn(Ⅱ) Metal-Organic Frameworks Based on Mn3 Clusters:From 2D Layer to 3D Framework by the “Pillaring” Approach[J]. CrystEngComm,2013,15(8):1613-1617.
[16]	Muthu S,Yip J H K,Vittal J J,et al. Coordination Networks of Ag(Ⅰ) and N,N'- Bis(3-pyridinecarboxamide)-1,6-hexane:Structures and Anion Exchange[J]. J Chem Soc,Dalton Trans,2002,(24):4561-4568.
[17]	Yi F Y,Yang W T,Sun Z M.Highly Selective Acetone Fluorescent Sensors Based on Microporous Cd(Ⅱ) Metal-Organic Frameworks[J]. J Mater Chem,2012,22(43):23201-23209.
[18]	Wan H G,Yang W T,Sun Z M.Mixed-Ligand Zn-MOFs for Highly Luminescent Sensing of Nitro Compounds[J]. Chem Asian J,2013,8(5):982-989.