新型三核配合物[CuL(DMF)_2]_2Zn(N_3)_2的合成及其性质
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摘要
以含草酰胺桥的单核配合物CuL(H_2L=2,3-二氧-5,6∶13,14-二联苯基-9,10-环己基-1,4,8,11-四氮杂十四环-7,12-二烯烃)为前驱体, Zn(ClO_4)_2·6H_2O为金属中心,NaN_3为辅助配体,DMF为溶剂,采用扩散法合成了一例新的三核金属配合物[CuL(DMF)_2]_2Zn(N_3)_2,并通过元素分析,X-射线粉末衍射、X-射线单晶衍射、红外光谱、紫外-可见光谱、磁性分析对其进行了表征。结构分析表明:该配合物(CCDC:1835721)属于三斜晶系,P-1空间群,晶胞参数分别为a=9.618 8(19)?,b=9.878 5(18)?,c=14.555(3)?,α=100.898(3)°,β=101.384(3)°,γ=109.661(3)°,V=1 226. 9(4)?~3,Z=1。磁性研究表明:配合物中顺磁金属离子Cu(Ⅱ)之间存在弱的反铁磁性相互作用。
Using a mononuclear ligand CuL(H_2L=2,3-dioxo-5,6 ∶13,14-dibenzo-9,10-(O)cyclohexyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene) containing oxamido bridge as the precursor ligand, Zn(ClO_4)_2·6 H_2O as metal center, NaN_3 as auxiliary ligand, DMF as solvent, a new trinuclear metal complex [CuL(DMF)_2]_2Zn(N_3)_2 was synthesized by diffusion method. The structure was characterized by elemental analysis, X-ray powder diffraction, X-ray single-crystal diffraction, IR, UV-Vis spectra, and magnetic analysis. The structural analysis showed the title complex(CCDC: 1835721) belongs to triclinic system and space group P-1 with cell parameters of a=9.618 8(19) ?, b=9.878 5(18) ?, c=14.555(3) ?, α=100.898(3)°, β=101.384(3)°, γ=109.661(3)°, V=1 226. 9(4) ?~3, Z=1. Magnetic susceptibility studies indicate the occurrence of weak antiferromagnetic coupling between the paramagnetic metals Cu(Ⅱ).
Using a mononuclear ligand CuL(H_2L=2,3-dioxo-5,6 ∶13,14-dibenzo-9,10-(O)cyclohexyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene) containing oxamido bridge as the precursor ligand, Zn(ClO_4)_2·6 H_2O as metal center, NaN_3 as auxiliary ligand, DMF as solvent, a new trinuclear metal complex [CuL(DMF)_2]_2Zn(N_3)_2 was synthesized by diffusion method. The structure was characterized by elemental analysis, X-ray powder diffraction, X-ray single-crystal diffraction, IR, UV-Vis spectra, and magnetic analysis. The structural analysis showed the title complex(CCDC: 1835721) belongs to triclinic system and space group P-1 with cell parameters of a=9.618 8(19) ?, b=9.878 5(18) ?, c=14.555(3) ?, α=100.898(3)°, β=101.384(3)°, γ=109.661(3)°, V=1 226. 9(4) ?~3, Z=1. Magnetic susceptibility studies indicate the occurrence of weak antiferromagnetic coupling between the paramagnetic metals Cu(Ⅱ).
引文
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[3] WANG X R,WANG X Z,LI Y,et al.Sonochemical synthesis of a multi-responsive regenerable water-stable zinc(II) fluorescent probe for highly selective,sensitive and real-time sensing of benzaldehyde,ferric ion and pH[J].Ultrason Sonochem,2018,44(7):340-349.
[4] 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(24):7399-7408.
[5] KIYONAGA T,HIGUCHI M,KAJIWARA T,et al.Dependence of crystal size on the catalytic performance of a porous coordination polymer[J].Chem Commun,2015,51(13):2728-2730.
[6] PHAN A,DOONAN C J,URIBE-ROMO F J,et al.Synthesis,structure,and carbon dioxide capture properties of zeolitic imidazolate frameworks[J].Acc Chem Res,2010,43(1):58-67.
[7] LIU X J,WANG X,XU J L,et al.Selective gas adsorption and fluorescence sensing response of a Zn(II) metal-organic framework constructed by a mixed-ligand strategy[J].Dalton Trans,2017,46(15):4893-4897.
[8] KETTNER F,WORCH C,MOELLMER J,et al.Synthesis,crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)](M2+=Fe2+,Co2+,Zn2+,Cd2+;tdc2-=2,5-thiophenedicarboxylate)[J].Inorg chem,2013,52(15):8738-8742.
[9] FENG X,FENG Y Q,GUO N,et al.Series d-f heteronuclear metal-organic frameworks:Color tunability and luminescent probe with switchable properties[J].Inorg Chem,2017,56(3):1714-1721.
[10] MARINESCUA G,ANDRUHB M,LLORET F,et al.Bis(oxalato)chromium(III) complexes:Versatile tectons in designing heterometallic coordination compounds[J].Coord Chem Rev,2011,255 (1):161-185.
[11] RUIZ R,FAUS J,LLORET F,et al.Coordination chemistry of N,N′-bis(coordinating group substituted) oxamides:A rational design of nuclearity tailored polynuclear complexes[J].Coord Chem Rev,1999,193-195(10):1069-1117.
[12] PEREIRA C L M,PEDROSO E F,STUMPF H O,et al.A CuIICoII Metallacyclophane-based metamagnet with a corrugated brick-wall sheet architecture[J].Angew Chem Int Ed,2004,43(8):956-958.
[13] SENGUPTA O,MUKHERJEE P S.Mixed azide and 5-(pyrimidyl)tetrazole bridged Co(II)/Mn(II) polymers:Synthesis,crystal structures,ferroelectric and magnetic behavior[J].Inorg Chem,2010,49(18):8583-8590.
[14] SHI W B,CUI A L,KOU H Z.Ligand-directed assembly of azide-bridged tetranuclear,one-dimensional and two-dimensional Cu(II) complexes:Synthesis,crystal structure and magnetic properties[J].Cryst Growth Des,2012,12(7):3436-3443.
[15] WANG X Y,WEI H Y,WANG Z M,et al.Formate-the analogue of azide:Structural and magnetic properties of M(HCOO)2(4,4′-bpy)·nH2O(M=Mn,Co,Ni;n=0,5)[J].Inorg Chem,2005,44(3):572-583.
[16] ZHANG Y H,WANG Q L,YANG G M.Synthesis,crystal structures and spectroscopic properties of two novel oxamido-bridged trinuclear complexes[Cu2M](M=Cu,Zn)[J].Trans Met Chem,2006,31(7):856-859.
[17] SHELDRICK G M.SAINT software reference manual;Siemens analytical X-ray systems[M].Madison,Wisconsin,USA,1996.
[18] SHELDRICK G M.SADABS,Program for empirical absorption correction of area detector data[M].University of G?ttingen,Germany,1996.
[19] SHELDRICK G M.SHELX-97,Program for X-ray crystal structure solution and refinement [M].University of G?ttingen,Germany,1997.
[20] GAO E Q,LIAO D Z,JIANG Z H,et al.Synthesis,crystal structure and magnetic properties of novel copper(II)-nickel(II) complexes of macrocyclic oxamides[J].Polyhedron,2001,20(10):923-927.
[21] WANNARIT N,SIRIWONG K,CHAICHIT N,et al.New series of triply bridged dinuclear Cu(II) compounds:Synthesis,crystal structure,magnetic properties,and theoretical study[J].Inorg Chem,2011,50(21):10648-10659.