两种具有螺旋结构的双核铜有机-无机配位聚合物的合成及表征

doi:10.7503/cjcu20150259

摘要/Abstract

摘要：

在水热和溶剂热条件下, 有机多齿羧酸4,4'-三苯胺二甲酸(H₂L)及含铜化合物分别与2,2'-联吡啶(bpy)和1,4-二(吡啶-4-甲氧基)苯(bpmb)反应, 合成了2种新型的含铜配位聚合物[Cu₂L(bpy)](1)和[CuL(bpmb)_0.5]·DMF(2). 通过X射线单晶衍射、红外光谱、元素分析、热重和粉末X射线衍射分析等对其结构进行了表征. 结果表明, 化合物1属正交晶系, Pnma空间群, 其骨架为二维层状结构; 化合物2属单斜晶系, P2₁/c空间群, 具有{4⁴·6¹⁰·8}拓扑结构的三维网络.

关键词: 4, 4'-三苯胺二甲酸, 配位聚合物, 螺旋结构, 水热合成, 溶剂热合成

Abstract:

Multidenate 4,4'-(phenylazanediyl)dibenzoic acid(H₂L) ligand and copper(Ⅱ) ions react with 2,2-bipyridine(bpy) under the hydrothermal conditions or 1,4-bis(pyridin-4-ylmethoxy)benzene(bpmb) under the solvothermal reactions. Two new coordination polymers, namely [Cu₂L(bpy)](1) and [CuL(bpmb)_0.5]·DMF(2), were obtained and characterized by single-crystal X-ray diffraction(XRD), Fourier transform infrared spectrosopy(FTIR) spectroscopy, elemental analyses, thermal analysis and power X-ray diffraction(PXRD). The results showed that the compound 1 displays orthorhombic crystal structure and exhibits two-dimensional(2D) layer architectures built with Pnma space group, and compound 2 crystallizes in the monoclinic space group P2₁/c and gives a 3D framework with {4⁴·6¹⁰·8} topology structure.

Key words: 4, 4-Dicarboxylic acid triphenylamine, Coordination polymer, Helical structure, Hydrothermal synthesis, Solventhermal synthesis

TrendMD:

赵仑, 张敏, 邓青辉, 王子忱. 两种具有螺旋结构的双核铜有机-无机配位聚合物的合成及表征. 高等学校化学学报, 2015, 36(8): 1455.

ZHAO Lun, ZHANG Min, DENG Qinghui, WANG Zichen. Synthesis and Characterization of Two Novel Cu(Ⅱ) Coordination Polymers with Helical Crystal Structure^†. Chem. J. Chinese Universities, 2015, 36(8): 1455.

图/表 6

Scheme 1 Synthetic routes and molecular structure of ligands and coordination modes of the carboxylic groups

Table 1 Crystal data and structure refinement of compounds 1 and 2

Compd.	1	2
CCDC No.	1047034	1047035
Formula	C₅₀H₃₄Cu₂N₄O₉	C₃₂H₂₇CuN₃O₆
Formula weight	961.89	613.11
Crystal system	Orthorhombic	Monoclinic
Space group	Pnma	P2₁/c
a/nm	1.15377(10)	1.2656(2)
b/nm	2.3293(2)	0.92408(15)
c/nm	1.62888(14)	2.5544(4)
α/(°)	90.00	90.00
β/(°)	90.00	96.158(4)
γ/(°)	90.00	90.00
V/nm³	4.3776(7)	6.4595(7)
Z	4	4
D_c/(g·cm^-3)	1.459	1.371
F(000)	1968.0	1268
GOF on F²	1.052	0.976
R₁/wR₂[I>2σ(I)]	0.0565/0.1369	0.0719/0.1972
R₁/wR₂(All data)	0.1084/0.1738	0.1462/0.2358

Fig.1 Crystal structures of compound 1(A) Coordination environment of the Cu(Ⅱ) ions in compound 1, the hydrogen atoms are omitted for clarity; (B) 2D net structure; (C) the helical chains in the (4,4) layers; (D) the helical chains.

Fig.2 Crystal structures of compound 2(A) Coordination environment of the Cu(Ⅱ) ions in compound 2, the hydrogen atoms are omitted for clarity; (B) 2D net structure;(C) the 3D framework; (D) the { 44·610·8} topology net; (E) the helical chains in the (4,4) layers; (F) the helical chains.

Fig.3 Experimental(a) and simulated(b) PXRD patterns of compounds 1(A) and 2(B)

Fig.4 TG curves of compounds 1(a) and 2(b)

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