Mg(Ⅱ)-Zn(Ⅱ)异金属配合物的结构设计与发光性质
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摘要
以吡啶-2,5-二羧酸为配体与MgCl_2·6H_2O和Zn(NO_3)_2·6H_2O,运用水热法在120℃下反应3 d,合成了一个混金属配合物,[Mg(H_2O)_6][Zn(pydc)_2]·2H_2O (1, H_2pydc=吡啶-2,5-二羧酸).并对配合物进行了X射线单晶衍射、X射线粉末衍射、红外光谱、热稳定性分析以及室温固态荧光光谱等表征.结果表明:配合物属于三斜晶系,■空间群,晶胞参数a=0.72725(10) nm,b=0.74311(10) nm,c=1.06859(15) nm,α=78.968(2)°,β=74.332(2)°,γ=70.428(2)°;V=0.52066(12) nm~3,Z=1.此配合物呈现深蓝色荧光.
A new heterometal complex [Mg(H_2O)_6][Zn(pydc)_2]·2 H_2O(1, H_2pydc=pyridine-2,5-dicarboxylic acid) was synthesized by hydrothermal reaction of pyridine-2, 5-dicarboxylic acid with MgCl_2·6 H_2O and Zn(NO_3)_2·6 H_2O at 120℃ for 3 days. The complexes were characterized by X-ray single crystal diffraction, X-ray powder diffraction, infrared spectroscopy, thermal stability analysis and room temperature solid-state fluorescence spectroscopy. The results showed that the complex crystallizes in triclinic system, space group ■, and the cell parameters are as follow: a=0.72725(10) nm, b=0.74311(10) nm, c=1.06859(15) nm, α=78.968(2)°, β=74.332(2)°, γ=70.428(2)°; V=0.52066(12) nm~3, Z=1. The complex exhibits dark-blue fluorescence.
A new heterometal complex [Mg(H_2O)_6][Zn(pydc)_2]·2 H_2O(1, H_2pydc=pyridine-2,5-dicarboxylic acid) was synthesized by hydrothermal reaction of pyridine-2, 5-dicarboxylic acid with MgCl_2·6 H_2O and Zn(NO_3)_2·6 H_2O at 120℃ for 3 days. The complexes were characterized by X-ray single crystal diffraction, X-ray powder diffraction, infrared spectroscopy, thermal stability analysis and room temperature solid-state fluorescence spectroscopy. The results showed that the complex crystallizes in triclinic system, space group ■, and the cell parameters are as follow: a=0.72725(10) nm, b=0.74311(10) nm, c=1.06859(15) nm, α=78.968(2)°, β=74.332(2)°, γ=70.428(2)°; V=0.52066(12) nm~3, Z=1. The complex exhibits dark-blue fluorescence.
引文
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[2] ZHANG,X F,DENG Z P,HUO L H,et al.Four alkali-induced 3D strontium(II) coordination polymers constructed from imidazole-4,5-dicarboxylate:syntheses,crystal structures,and properties[J].Eur J Inorg Chem,2012,2012(33):5506-5514.
[3] FROMM K M,GUENEAU E D.Structures of alkali and alkaline earth metal clusters with oxygen donor ligands[J].Polyhedron,2004,23(9),1479-1504.
[4] FROMM K M.Coordination polymer networks with s-block metal ions[J].Coord Chem Rev,2008,252(8-9):856-885.
[5] ZHANG C X,ZHANG Y,YANG,Y.Synthesis,characterization and crystal structure of a novel three-dimensional supramolecular architecture formed by manganese(II) and pyridine-2,5-dicarboxylic acid[J].J Coord Chem,2006,59(4):389-393.
[6] LIANG Y,CAO R,SU W,et al.Syntheses,structures,and magnetic porperties of two gadolinium(III)-copper(II) coordination polymers by a hydrothermal reaction[J].Angew Chem Int Ed,2000,39(18):3304-3307.
[7] WIBOWO A C,SMITH M D,ZUR LOYE H C.Structural diversity of metal-organic materials containing bismuth(III) and pyridine-2,5-dicarboxylate[J].Cryst Growth Des,2011,11(10):4449-4457.
[8] SAHA D,MAITY T,DEY T,et al.One-dimensional chain copper(II) complex:synthesis,X-ray crystal structure and catalytic activity in the epoxidation of styrene[J].Polyhedron,2012,35(1):55-61.
[9] SAHA D,SEN R,MAITY T,et al.Porous magnesium carboxylate framework:synthesis,X-ray crystal structure,gas adsorption property and heterogeneous catalytic aldol condensation reaction[J].Dalton Trans,2012,41:7399-7408.
[10] SAHA D,HAZRA D K,MAITY T,et al.Heterometallic metal-organic frameworks that catalyze two different reactions sequentially[J].Inorg Chem,2016,55:5729-5731.
[11] SAHA D,GAYEN S,KONE S.Cu(II)/Cu(II)-Mg(II) containing pyridine-2,5-dicarboxylate frameworks:Synthesis,structural diversity,inter-conversion and heterogrneous catalytic epoxidation[J].Polyhedron,2018,146:93-98.
[12] SHELDRICK G M.SHELXS-2014,Program for Crystal Structure Solution[M].G?ttingen:University of G?ttingen,2014.
[13] SHELDRICK G M.Crystal structure refinement with SHELXL[J].Acta Crystallogrc Struct Chem,2015,71(1):3-8.
[14] CHEN Y M,SHE S X,GAO Q,et al.Synthesis,structures and properties of the first series of SrII-MII (M=Cu,Co,Ni and Zn) coordination polymers based on pyridine-2,5-dicarboxylic acid[J].CrystEngComm,2014,16:1091-1102.
[15] CHEN Y M,GAO Q,ZHANG H F,et al.Five heterometallic SrII-MII (M=Co,Ni,Zn,Cu) 3-D coordination polymers:synthesis,structures and magnetic properties[J].Polyhedron,2014,71:91-98.
[16] SMITH G,WERMUTH U D.The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg,Ca,Sr and Ba) of (4-aminophenyl) arsonic acid[J].Acta Crystallogr C Struct Chem,2017,73(1):61-67.
[17] FUJII K,SOGAWA M,YOSHIMOTO N,et al.Structural study on magnesium ion solvation in diglyme-based electrolytes:IR spectroscopy and DFT calculations[J].J Phy Chem B,2018,122(37):8712-8717.
[18] ZHAO B,GAO H L,CHEN X Y,et al.A promising MgII-Ion-selective luminescent probe:structures and properties of Dy-Mn polymers with high symmetry[J].Chem Eur J,2006,12:149-158.
[19] ALLENDORF M D,BAUER C A,BHAKTA R K,et al.Luminescent metal-organic frameworks[J].Chem Soc Rev,2009,38(5):1330-1352.
[20] DU M,JIANG X J,ZHAO X J.Molecular tectonics of mixed-ligand metal-organic frameworks:positional isomeric effect,metal-directed assembly,and structural diversification[J].Inorg Chem,2007,46(10):3984-3995.
[21] LIN X Y,ZHAO L M,WANG D H,et al.Structural diversities of squarate-based complexes:photocurrent responses and thermochromic behaviours enchanced by viologens[J].Inorg Chem Front,2018,5(1):189-199.
[22] 区泳聪,钟均星,宋萦怡,等.两个基于2,2’-联吡啶-5,5’-二羧酸配体构筑的碱土金属配合物的合成、晶体结构及其光致发光性质[J].无机化学学报,2016,32(4):738-744.OU Y C,ZHONG J X,SONG,Y Y,et al.Two 1D chain structures derived from alkaline-earth metal complexes and 2,2’-bipyridine-5,5’-dicarboxylate ligand:syntheses,crystal structures and luminescent properties[J].Chinese Journal of Inorganic Chemistry,2016,32(4):738-744.(Ch).