由醋酸根桥连构筑的零维六核镉(Ⅱ)格子型配合物和一维锌(Ⅱ)配位聚合物的合成、晶体结构及荧光性质
Syntheses, Crystal Structures, and Fluorescence Properties of 0D Hexanuclear Cadmium(Ⅱ) Grid Complex and 1D Zinc(Ⅱ) Coordination Polymer Constructed by Acetate-Bridge
作者单位E-mail
鲁圣楠 华侨大学材料科学与工程学院, 厦门 361021  
吴文士 华侨大学材料科学与工程学院, 厦门 361021 wws@hqu.edu.cn 
石凤湘 华侨大学材料科学与工程学院, 厦门 361021  
全志龙 华侨大学材料科学与工程学院, 厦门 361021  
摘要: 采用普通溶液法合成了配合物[Cd6(Tppahz)2(Ac)2(H2O)6]5H2O(1)和{[Zn1.5(Tppahz)0.5](Ac)2}n2)(Tppahz=N,N'-二(吡啶-2'-甲缩)-2,6-吡啶二甲酰肼),并通过X射线单晶衍射分析、X射线粉末衍射分析、红外光谱分析和热重分析等对配合物的结构进行了测定。结果分析表明:配合物1是格子型结构,三斜晶系,P1空间群,Cd(Ⅱ)离子与周围原子采用N2O5,N3O4两种不同的配位类型,形成扭曲的五角双锥构型;配位聚合物2是一维链状结构,单斜晶系,C2/c空间群,Zn(Ⅱ)离子与周围原子采用N3O2,N2O3两种不同的配位类型,形成畸变的四角锥配位构型。配位聚合物2通过π-π堆积作用形成了三维超分子结构。在室温下研究了2个配合物的荧光性质。荧光分析表明,配体Tppahz与d10过渡金属离子配位后其荧光发生了红移。
关键词: 席夫碱  格子型配合物  晶体结构  荧光性质
基金项目: 福建省工业引导性(重点)项目(No.2017H0018)和华侨大学研究生科研创新能力培养计划资助
Abstract: Two new metal-organic complexes, namely[Cd6(Tppahz)2(Ac)2(H2O)6]·5H2O (1) and {[Zn1.5(Tppahz)0.5](Ac)2}n (2), have been constructed from organic ligand N,N'-bis(pyridine-2'-methyl)-2,6-pyridinedicarboxylic acid hydrazide and d10 transition metals. The structures of complexes 1 and 2 are determined and characterized by single-crystal X-ray analysis, XRD powder diffraction analysis, infrared spectroscopy, thermal stability analysis and fluorescence analysis method. The crystal structural analysis reveals that the complex 1 belongs to triclinic system, space group P1 and the whole molecule presents grid structure, the surrounding coordination atoms around the Cd(Ⅱ) ions adopt two different coordination types of N2O5 and N3O4 to form a twisted pentagonal bipyramidal configuration. The complex 2 is a one-dimensional chain structure, belongs to monoclinic system, and space group C2/c, the surrounding coordination atoms around the Zn(Ⅱ) ions adopt two different coordination types of N3O2 and N2O3 to form a distorted octahedral coordination geometry. Complex 2 forms a three-dimensional supramolecular structure through π-π stacking. In addition, fluorescent properties of these complexes were investigated at room temperature. The fluorescence spectroscopic analysis demonstrated the red-shifted phenomenon of ligand Tppahz after coordinated with d10 transition metals.
Keywords: Schiff base  grid complex  crystal structure  fluorescence property
投稿时间:2018-11-17 修订日期:2019-03-03
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鲁圣楠,吴文士,石凤湘,全志龙.由醋酸根桥连构筑的零维六核镉(Ⅱ)格子型配合物和一维锌(Ⅱ)配位聚合物的合成、晶体结构及荧光性质[J].无机化学学报,2019,35(5):837-843.
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