Metal-organic frameworks constructed from 2,4,6-Tris(4-pyridyl)-1,3,5-triazine.
Metal-organic frameworks constructed from 2,4,6-Tris(4-pyridyl)-1,3,5-triazine.
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DOI：
10.1021/ic701346x
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发表时间：
2008-05
影响因子：
4.6
通讯作者：
Ming-Xing Li;Zhiwei Miao;M. Shao;Shengwen Liang;Shourong Zhu
中科院分区：
文献类型：
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作者：
Ming-Xing Li;Zhiwei Miao;M. Shao;Shengwen Liang;Shourong Zhu
水热合成了五种基于2,4,6-三(4-吡啶基)-1,3,5-三嗪(tpt)配体的新型金属有机骨架。 tpt 和 AgNO 3 在酸性溶液中于 180 ℃ 反应生成 {[Ag(Htpt)(NO3)]NO(3).4H2O}n (1)。Ag(I) 由两个吡啶基氮和一个硝基氧三角配位，形成一维锯齿状链。 tpt 与 CuSO4 反应得到 {[Cu2(tpt)2(SO4)2(H2O)2].4H2O}n (2)。铜(II)与两个吡啶基氮、两个硫酸根氧和两个水氧原子键合，形成细长的八面体几何形状。每个 H2O 配体桥接两个铜 (II)，而硫酸盐通过 micro-1,3 和 micro-1,1 方式桥接铜 (II)。硫酸铜(II)-H2O2D层通过双齿tpt连接形成3D聚合结构。 Cu(SO4)2、tpt 和 1,2,4,5-苯四甲酸 (H4btec) 在哌啶存在下反应，生成 [Cu(tpt)(H2btec)1/2]n (3)。铜(I)处于三角锥配位环境中，由tpt的三个吡啶基氮在平面上配位，而羧酸氧与铜(I)轴向配位。 tpt-Cu形成层，各层通过H 2btec2- 连接形成二维双层配位聚合物。在合成中用 ZnI2 代替 CuSO4 得到 {[Zn(tpt)(btec)1/2].H2O}n (4)。锌(II)具有扭曲的四面体几何形状，并通过二齿tpt和外四齿btec4-连接形成二维配位网格。 tpt 与 CuCN 的反应导致组装 3D 金属有机骨架 [Cu3(CN)3(tpt)]n (5)。铜（I）由一个吡啶基氮和两个氰化物三角配位，形成有趣的蜂窝结构。发光研究表明1、3、4和5具有蓝色荧光，可以将其指定为配体中心发射。热分析表明，所有这些配合物都相当稳定，特别是4，框架在高达430摄氏度的温度下保持稳定。
Five new metal-organic frameworks based on 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) ligand have been hydrothermally synthesized. Reaction of tpt and AgNO 3 in an acidic solution at 180 degrees C yields {[Ag(Htpt)(NO3)]NO(3).4H2O}n (1).Ag(I) is trigonally coordinated by two pyridyl nitrogen and one nitrato oxygen to form a 1D zigzag chain. Reaction of tpt with CuSO4 affords {[Cu2(tpt)2(SO4)2(H2O)2].4H2O}n (2). Copper(II) is bonded to two pyridyl nitrogen, two sulfato oxygen, and two water oxygen atoms to form an elongated octahedral geometry. Each H2O ligand bridges two copper(II), whereas sulfate bridges copper(II) via micro-1,3 and micro-1,1 fashions. The copper(II)-sulfate-H2O2D layers are linked by bidentate tpt to form a 3D polymeric structure. Reaction of Cu(SO4)2, tpt, and 1,2,4,5-benzenetetracarboxylic acid (H4btec) in the presence of piperidine gives [Cu(tpt)(H2btec)1/2]n (3). Copper(I) is located in a trigonal-pyramidal coordination environment and coordinated by three pyridyl nitrogen of tpt in a plane, whereas a carboxylate oxygen is coordinated to the copper(I) axially. The tpt-Cu forms a layer, and the layers are linked through H 2btec2- to form a 2D double-layered coordination polymer. Replacing CuSO4 with ZnI2 in the synthesis gives {[Zn(tpt)(btec)1/2].H2O}n (4). Zinc(II) is in a distorted tetrahedral geometry and linked through bidentate tpt and exotetradentate btec4- to form a 2D coordination grid. Reaction of tpt with CuCN leads to the assembly of a 3D metal-organic framework [Cu3(CN)3(tpt)]n (5). Copper(I) is trigonally coordinated by one pyridyl nitrogen and two cyanides to form an intriguing honeycomb architecture. Luminescence study shows that 1, 3, 4, and 5 have blue fluorescence, which can be assigned to be ligand-centered emissions. Thermal analysis shows that all of these complexes are quite stable, and especially for 4, the framework is stable up to 430 degrees C.