八氰钨-钴异金属配合物的合成、结构和理论研究
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摘要
以八氰钨为构筑单元,与过渡金属Co~Ⅱ离子合成了一个具有三维结构的八氰钨-钴配位聚合物Co_2~Ⅱ(4-Mepy)8[W~Ⅳ(CN)_8](4-Mepy=4-甲基吡啶)。通过X-射线单晶衍射、元素分析和红外光谱对标题配合物进行了结构表征。单晶结构解析表明,标题配合物属于正交晶系,Fddd空间群,部分晶体学参数为:a=13. 939(4)■,b=26. 397(7)■,c=30. 168(8)■,V=11 100(5)■3,z=8,Dc=1. 502 g/cm~3,μ=2. 711 mm~(-1),F(000)=5 056,R=0. 046 8[I>2σ(I)],wR=0. 106 2[I>2σ(I)]。Co~Ⅱ离子中心均处于压缩Co N6八面体中,CoⅡ和WⅣ离子通过4个CN基团与相邻异金属W彼此交替相连,形成三维网状结构。此外,基于密度泛函理论(DFT)对八氰钨-钴配位聚合物进行了量子化学计算,计算结果与实验吻合。
The title complex with the general formula Co_2~Ⅱ( 4-Mepy)8[WⅣ( CN)8](4-Mepy= 4-methylpyridine) has been synthesized and confirmed by single crystal X-ray diffraction,elemental analysis and infrared spectrum. Single crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic,Fddd space group with a = 13. 939( 4)■,b = 26. 397( 7)■,c = 30. 168( 8)■,V = 11 100( 5) ■3,z= 8,Dc= 1. 502 g/cm~3,μ= 2. 711 mm~(-1),F( 000) = 5 056,R= 0. 046 8 and wR= 0. 106 2 with I>2σ( I).CoⅡions lie in the center of the compressed CoN_6 octahedron in title complex,Co~Ⅱ and W~Ⅳ ions are alternately bridged by cyano groups forming a three dimension bimetallic framework.The quantum calculation of the title complex has been performed by density functional theory method.The results of the calculation are consistent with the experiments.
The title complex with the general formula Co_2~Ⅱ( 4-Mepy)8[WⅣ( CN)8](4-Mepy= 4-methylpyridine) has been synthesized and confirmed by single crystal X-ray diffraction,elemental analysis and infrared spectrum. Single crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic,Fddd space group with a = 13. 939( 4)■,b = 26. 397( 7)■,c = 30. 168( 8)■,V = 11 100( 5) ■3,z= 8,Dc= 1. 502 g/cm~3,μ= 2. 711 mm~(-1),F( 000) = 5 056,R= 0. 046 8 and wR= 0. 106 2 with I>2σ( I).CoⅡions lie in the center of the compressed CoN_6 octahedron in title complex,Co~Ⅱ and W~Ⅳ ions are alternately bridged by cyano groups forming a three dimension bimetallic framework.The quantum calculation of the title complex has been performed by density functional theory method.The results of the calculation are consistent with the experiments.
引文
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[8]NOWICKA B,KORZENIAK T,STEFA'NCZYK O,et al.The impact of ligands upon topology and functionality of octacyanidometallate-based assemblies[J].Coord.Chem.Rev.,2012,256(17/18):1 946-1 971.
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[10]WEI R M,KONG M,CAO F,et al.Water induced spincrossover behaviour and magneto-structural correlation inoctacyanotungstate(Ⅳ)-based iron(Ⅱ)complexes[J].Dalton Trans.,2016,45(46):18 643-18 652.
[11]HERRERA J M,MARVAUD V,VERDAGUER M,et al.Reversible photoinduced magnetic properties in the heptanuclear complex[MoⅣ(CN)2(CN-CuL)6]8+:a photomagnetic high-spin molecule[J].Angew.Chem.Int.Ed.,2004,43(41):5 468-5 471.
[12]LEIPOLDT J G,BOK L D C,CILLIERS P J.The preparation of potassiumoctacyanotungstate(Ⅳ)dihydrate[J].Z.Anorg.Allg.Chem.,1974,407(3):350-352.
[13]BOK L D C,LEIPOLDT J D,BASSON S S.The preparation of Cs3Mo(CN)8·2H2O and Cs3W(CN)8·2H2O[J].Z.Anorg.Allg.Chem.,1975,415(1):81-83.
[14]SIEMENS.SAINT Software Reference Manual,Siemens Energy&Automation,Inc[CP].Madison,Wisconsin,USA,1994.
[15]KRAUSE L,HERBST-IRMER R,SHELDRICK G M,et al.Comparison of silver and molybdenum microfocus,X-ray sources for single-crystal structure determination[J].J.Appl.Crystallogr.,2015,48:3-10.
[16]SHELDRICK G.Crystal structure refinement with SHELXL[J].Acta Crystallogr.,Sect.C:Cryst.Struct.Commun.,2015,71:3-8.
[17]SHELDRICK G.SHELXT-Integrated space-group and crystal-structure determination[J].Acta Crystallogr.,Sect.A:Fundam.Crystallogr.,2015,71:3-8.
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[19]LLUNELL M,CASANOVA D,CIRERA J,et al.SHAPE(Version 2.1)[CP].Universitat de Barcelona,2013.