Construction of diverse CdII/ZnII coordination polymers based on 5-(quinolyl)tetrazolate generated via in situ hydrothermal synthesis
Construction of diverse CdII/ZnII coordination polymers based on 5-(quinolyl)tetrazolate generated via in situ hydrothermal synthesis
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DOI：
10.1039/c2ce26323h
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发表时间：
2013-01
期刊：
影响因子：
3.1
通讯作者：
Li Ma;Naiqian Yu;Susu Chen;H. Deng
中科院分区：
文献类型：
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作者：
Li Ma;Naiqian Yu;Susu Chen;H. Deng
通过改变反应参数，如金属盐和二级配体，得到了一系列新的配位聚合物，[Cd(QTZ)2] (1), [Cd(QTZ)N3·H2O] (2), [Zn(QTZ)Cl] (3), [Cd2(QTZ)2(INA)2]·0.25H2O (4), [Cd2(QTZ)（btrc）·2(H2O)]·1.67H2O (5), 2[Cd3(QTZ)2（btec）·H2O]·H2O (6) (QTZ = 5-（喹啉基）四唑；异烟酸；H3btrc = 1,3,5-苯三羧酸；在水热反应下成功合成了H4btec = 1,2,4,5-苯四羧酸)，并用x射线单晶衍射对其结构进行了表征。这些化合物中的QTZ配体是由3-喹啉碳腈和NaN3在水中与CdII/ ni盐的酸[2 + 3]环加成反应原位生成的。化合物1显示具有Schlafli符号66的三维（3D） 2重互穿金刚石网络。化合物2是由无限的Cd-N3 -链和QTZ配体构成的二维配位框架。化合物3呈现由Zn2(QTZ)2Cl2亚基互连而成的4-连接二维（4,4）网。化合物4是由Cd2(QTZ)2(INA)2亚基与Cd2(QTZ)2亚基相互连接而成的二维骨架。化合物5呈二维层状结构，Cd2-QTZ链被btrc配体扩展。在化合物6中，三核CdII簇通过对QTZ配体相互连接，形成无限之字形Cd3-QTZ链；此外，相邻的Cd3-QTZ链被btec配体扩展，形成三维网络。这些结果表明，QTZ是一种强大的功能配体，二级配体和过渡金属离子的性质在控制分子自组装结构中也起着重要作用。此外，还研究了所有化合物在室温下的固态发光特性。
By variation of reaction parameters such as metal salts and secondary ligands, a series of new coordination polymers, [Cd(QTZ)2] (1), [Cd(QTZ)N3·H2O] (2), [Zn(QTZ)Cl] (3), [Cd2(QTZ)2(INA)2]·0.25H2O (4), [Cd2(QTZ)(btrc)·2(H2O)]·1.67H2O (5), 2[Cd3(QTZ)2(btec)·H2O]·H2O (6) (QTZ = 5-(quinolyl)tetrazole; HINA = isonicotinic acid; H3btrc = 1,3,5-benzenetricarboxylic acid; H4btec = 1,2,4,5-benzenetetracarboxylic acid) were successfully synthesized under hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction. The QTZ ligands in these compounds are in situ generated from a [2 + 3] cycloaddition reaction of 3-quinolinecarbonitrile and NaN3 in water with the acid of CdII/ZnII salt. Compound 1 displays a three-dimensional (3D) 2-fold interpenetrating diamond network with Schlafli symbol 66. Compound 2 represents a two-dimensional (2D) coordination framework constructed of infinite Cd–N3− chains and QTZ ligands. Compound 3 exhibits a 4-connected 2D (4,4) net built up by interconnection of Zn2(QTZ)2Cl2 subunits. Compound 4 is a 2D framework constructed by interconnection of Cd2(QTZ)2(INA)2 subunit and Cd2(QTZ)2 subunit. Compound 5 exhibits a 2D layered structure with the Cd2–QTZ chain extended by btrc ligands. In compound 6, trinuclear CdII clusters link each other by pairs of QTZ ligands to form an infinite zigzag Cd3–QTZ chain; furthermore the adjacent Cd3–QTZ chains are extended by the btec ligands to form a 3D network. These results indicate that QTZ is a powerful functional ligand and the nature of secondary ligands and transition metal ions also play significant roles in dominating molecular self-assembled structure. In addition, the luminescent properties of all compounds have been investigated in the solid state at room temperature.