一维链式三唑锰晶体的结构及磁性能研究
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摘要
用1H-1,2,4-三唑-3,5-二羧酸(H3dctrz)为配体,1,2,4,5-苯四羧酸(H4btec)为辅助生长剂,设计合成了一维链式配合物[Mn(Hdctrz)(H2O)3)]n,通过元素分析,红外光谱和粉末衍射进行了常规表征,同步辐射光源衍射结构分析给出该配合物结晶于单斜晶系空间群P21/c,其中Mn离子与N、O原子采取稍微扭曲的八面体构型,相邻的锰离子通过μ1,4-Hdctrz桥联形成一维"之"字型结构,氢键在构筑与稳定三维网状结构起重要作用。变温磁化率测定表明该配合物中两个金属锰之间表现为弱的反铁磁作用(J=-0.0599(2)cm-1)。
One dimension chain complex [Mn( Hdctrz)( H2O)3]n,(1) based on the self-assembly of Mn2 +ions with 1H-1,2,4-triazole-3,5-dicarboxylic acid(H3dctrz),1,2,4,5-benzenetetracarboxylic acid(H4btec) has been synthesized and characterized by synchrotron radiation X-Ray diffraction(SR-XRD),elemental analysis,IR,powder XRD. Crystal structural analysis reveals that the complex crystallizes in monoclinic system with space group P21/c. The coordinated environment of Mn2 +displays a slightly distorted octahedral geometry. The adjacent Mn2 +ions are linked by a μ1,4-Hdctrz bridge forming one dimensional zigzag chains. Further,these 1D chains form 3D networks by intermolecular hydrogen bonds. Variable temperature magnetic properties have been investigated and indicated a weak antiferromagnetic coupling interaction between the Mn(Ⅱ) centres in complex 1 with a value of J =- 0.0599(2) cm-1.
One dimension chain complex [Mn( Hdctrz)( H2O)3]n,(1) based on the self-assembly of Mn2 +ions with 1H-1,2,4-triazole-3,5-dicarboxylic acid(H3dctrz),1,2,4,5-benzenetetracarboxylic acid(H4btec) has been synthesized and characterized by synchrotron radiation X-Ray diffraction(SR-XRD),elemental analysis,IR,powder XRD. Crystal structural analysis reveals that the complex crystallizes in monoclinic system with space group P21/c. The coordinated environment of Mn2 +displays a slightly distorted octahedral geometry. The adjacent Mn2 +ions are linked by a μ1,4-Hdctrz bridge forming one dimensional zigzag chains. Further,these 1D chains form 3D networks by intermolecular hydrogen bonds. Variable temperature magnetic properties have been investigated and indicated a weak antiferromagnetic coupling interaction between the Mn(Ⅱ) centres in complex 1 with a value of J =- 0.0599(2) cm-1.
引文
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[4]Zhou S M,Yuan S J,Wang L,et al.Positive Isotropic Resonance Field Shift of Exchange Coupled Wedgedpermalloy/FeMn Bilayers[J].Appl.Phys.Lett.,2003,83:2013-2015.
[5]Zhang J P,Zhang Y B,Lin J B,et al.Metal Azolate Frameworks:from Crystal Engineering to Functional Materials[J].Chem.Rev.,2012,112(2):1001-1033.
[6]AromíG,Barrios L A,Roubeau O,et al.Triazoles and Tetrazoles:Prime Ligands to Generate Remarkable Coordination Materials[J].Coord.Chem.Rev.,2011,255(5-6):485-546.
[7]Ma Q,Zhu M L,Lu L P,et al.Trinuclear-based Coordination Compounds of Mn(Ⅱ)and Co(Ⅱ)with4-amino-3,5-dimethyl-1,2,4-triazole and Azide and Thiocyanate Anions:Synthesis,Structure and Magnetic Properties[J].Inorg Chim Acta,2011,370(1):102-107.
[8]Ma Q,Zhu M L,Lu L P,et al.Synthesis and Characterisation of Mn(Ⅱ),Co(Ⅱ)and Cd(Ⅱ)Coordination Polymers of 1,2,4-triazole-3,5-dicarboxylic Acid[J].Dalton Trans.,2010,39(25):5877-5884.
[9]Baitalik S,Dutta B,Nag K.Spectroscopic and Redox Properties of Rh(Ⅲ)Ru(Ⅱ)and Ru(Ⅱ)Ru(Ⅱ)Complexes Derived from 2,2'-bipyridine,Pyrazole-3,5-bis(benzimidazole)and 1,2,4-triazole-3,5-dicarboxylic Acid as Bridging Ligands[J].Polyhedron,2004,23(6):913-919.
[10]Otwinowski Z,W M Processing of X-ray Diffraction Data Collected in Oscillation Mode[J].Method Enzymo,1997,276(1):307-326.
[11]Sheldrick G M.A Short History of SHELX[J].Acta Cryst,2008,A64(1):112-122.
[12]Deacon G B,Phillips R J.Relationships between the Carbon-oxygen Stretching Frequencies of Carboxylato Complexes and the type of Carboxylate Coordination[J].Coord.Chem.Rev.,1980,33:227-250.
[13]Sun Y Y,Zhang Y W,Zhang G,et al.Catena-Poly[[triaqua-zinc(Ⅱ)]-mu-1H-1,2,4-triazole-3,5-dicarboxylato][J].Acta Cryst.Sec.E,2008,64(9):m1113-m1122.
[14]Fisher M E.Magnetism in One-Dimensional Systems-the Heisenberg Model for Infinite Spin[J].Am.J.Phys.,1964,32:343-346.