由多酸无机链及金属-有机链构筑的一个新型Anderson超分子化合物
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摘要
选用柔性双(三氮唑)有机配体1,6-双(1,2,4-三氮唑-1-y1)己烷(btx),利用水热技术合成一例新的基于Anderson型多酸的超分子化合物,{Cu~Ⅱ(btx)Na_2(H_2O)_8[H_2Cr(OH)_6Mo_6O_(18)]}·[Cr(OH)_6Mo_6O_(18)]·16H_2O (1).化合物1的结构利用红外光谱、元素分析和单晶X-射线进行了表征.化合物1包含两种结构亚单元:Anderson多阴离子通过Na(H_2O)~(6+)片段连接成的一维多酸无机链以及配体btx通过Cu2+离子连接成的金属-有机链.多酸无机链以及金属-有机链相互连接形成一个网格状的二维层结构.化合物1中游离的Anderson多阴离子通过氢键作用力将相邻的二维网格层连接成一个三维超分子框架结构.同时我们又研究了化合物1的光催化和电化学性质,并且1-CPE可用于亚硝酸钾安培传感器.
A novel supramolecular compound based on Anderson type polyoxomatelate,{CuⅡ(btx)Na_2(H_2O)_8[H_2Cr(OH)_6Mo_6O_(18)]}·[Cr(OH)_6Mo_6O_(18)]·16H_2O(1) was synthesized by hydrothermal method using a flexible bis(triazole) organic ligand 1,6-bis(1,2,4-triazole-1-y1) hexane(btx).The structure of 1 was characterized by IR,element analysis and single crystal X-ray diffraction.Compound 1 consists of two structural subunits:the one-dimensional POM chain of Anderson anions linked by Na(H_2O)~(6+)fragments and the metal-organic chain of ligands btx linked by Cu2+ions.The POM inorganic chains and the metal-organic chains are interconnected to form a two-dimensional lattice structure.The dissociative Anderson polyanions connect adjacent two-dimensional grid layers to form a three-dimensional supramolecular framework through hydrogen bonding forces.Photocatalytic and electrochemical properties of compound 1 were also investigated.1-CPE can be used as a potassium nitrite amperometric sensor.
A novel supramolecular compound based on Anderson type polyoxomatelate,{CuⅡ(btx)Na_2(H_2O)_8[H_2Cr(OH)_6Mo_6O_(18)]}·[Cr(OH)_6Mo_6O_(18)]·16H_2O(1) was synthesized by hydrothermal method using a flexible bis(triazole) organic ligand 1,6-bis(1,2,4-triazole-1-y1) hexane(btx).The structure of 1 was characterized by IR,element analysis and single crystal X-ray diffraction.Compound 1 consists of two structural subunits:the one-dimensional POM chain of Anderson anions linked by Na(H_2O)~(6+)fragments and the metal-organic chain of ligands btx linked by Cu2+ions.The POM inorganic chains and the metal-organic chains are interconnected to form a two-dimensional lattice structure.The dissociative Anderson polyanions connect adjacent two-dimensional grid layers to form a three-dimensional supramolecular framework through hydrogen bonding forces.Photocatalytic and electrochemical properties of compound 1 were also investigated.1-CPE can be used as a potassium nitrite amperometric sensor.
引文
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[2]YU R M,KUANG X F,WU X Y,et al.Stabilization and immobilization of polyoxometalates in porous coordination polymers through host-guest interactions[J].Coordination Chemistry Reviews,2009,253(23):2872-2890.
[3]UDALOVA L I,ADONIN S A,ABRAMOV P A,et al.Complexes of non-lacunary keggin-and dawson-type polyoxometalates with Pb(II):formation of 1d coordination polymers with different bonding modes[J].New Journal of Chemistry,2016,40(12):9981-9985.
[4]WAN R,MA P T,HAN M D,et al.Discovery and isolation of the trans-isomers of two 1:2-type lanthanide-containing monolacunary dawson-type tungstophosphates:[LnIII(α2-P2W17O61)2]17-(Ln=La,Ce)[J].Dalton Transactions,2017,46(16):5398-5405.
[5]JASSAL A K,RANA L K,HUNDAL G.Structure directing role of amines and water molecules in the self-assembly of polyoxomolybdates[J].Chemical Engineering Communications,2017,19(15):2021-2035.
[6]SHIVAIAH V,CHATTERJEE T,SRINIVASU K,et al.A water pipe held up by a polyoxometalate supported transition metal complex:synthesis and characterization of[Cu2(phen)2(CH3COO)(CH3COOH)(H2O)2][Al(OH)6Mo6O18]·28H2O[J].European Journal of Inorganic Chemistry,2007,2:231-234.
[7]WANG X L,CHANG Z H,LIN H Y,et al.Assembly and photocatalysis of two novel 3d Anderson-type polyoxometalate-based metal-organic frameworks constructed from isomeric bis(pyridylformyl)piperazine ligand[J].Dalton Transactions,2014,43(32):12272-12278.
[8]NOMIYA K,TAKAHASHI T,SHIRAI T,et al.Anderson-type heteropolyanions of molybdenum(VI)and tungsten(VI)[J].Polyhedron,1987,6(2):213-218.
[9]BLESSING R.An empirical correction for absorption anisotropy[J].Acta Crystallographica,1995,(51):33-38.
[10]SHELDRICK G M.A short history of SHELX[J].Acta Crystallographica Section A,2008,64(1):112-122.
[11]ZHANG P P,PENG J,TIAN A X,et al.A series of compounds based on the anderson-type polyoxoanions and cu-amino acid complexes[J].Journal of Molecular Structure,2009,931(1):50-54.
[12]杨状,陶东平,王舰,等.BiVO4光催化降解黄药的实验研究[J].辽宁科技大学学报,2017,40(5):368-372
[13]刘晓芳,张衡,杨松,等.金属有机框架材料的特性、制备方法及应用研究进展[J].贵州大学学报(自然科学版),2015,32(4):15-19.
[14]WANG X L,SUN J J,LIN H Y,et al.pH-tuned diverse structures and properties:two anderson-type polyoxometalate-based metal-organic complexes for selective photocatalysis and adsorption of organic dyes[J].RSC advances,2016,6(112),110583-11059.