Metal–organic frameworks with oxazoline-containing tripodal ligand: structure changes via reaction medium and metal-to-ligand ratio
Metal–organic frameworks with oxazoline-containing tripodal ligand: structure changes via reaction medium and metal-to-ligand ratio
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DOI：
10.1039/c002874f
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发表时间：
2010-11
期刊：
影响因子：
3.1
通讯作者：
Yong-Qing Huang;Zhongliang Shen;Xia-Ying Zhou;T. Okamura;Zhi Su;Jian Fan;Wei‐Yin Sun;jin-quan yu;N. Ueyama
中科院分区：
文献类型：
--
作者：
Yong-Qing Huang;Zhongliang Shen;Xia-Ying Zhou;T. Okamura;Zhi Su;Jian Fan;Wei‐Yin Sun;jin-quan yu;N. Ueyama
合成了六个新的铜配合物[Cu_2（L）_2（H_2 O）]（Cl_4）_2（1），[Cu_3（L）_2（CH_3CN）_3（Cl_4）]（2），[Cu_2（L）_2Cl] Cl_4·（9/4）H_2 O·（3/4）CH_3CN（3），[Cu_2（L）_2（CH_3CN）_2]（Cl_4）_2·2 H_2 O（4），[Cu_2（L）_Br_2]（5）和[Cu_4（L）_2Br_4]·2CH_3CN（6）[L = 1，3，5-三（2-恶唑啉基）苯]的合成。采用相同的反应物，不同的溶剂得到的配合物1和2分别具有一维链状和三核螺旋桨状的M3 L2笼状结构。通过CuCl和CuBr的加成，分别合成了具有二维（42·62·82）（4·62）（4·62）拓扑网络和M2 L2大环结构的化合物3和4。通过改变金属与配体的比例，分离出了具有不同结构的配合物5和6。5是无限一维链，而6是具有（4·122）2（42·124）拓扑的3D框架。结果表明，反应溶剂，抗衡阴离子和金属与配体的比例在框架的形成中起重要作用。通过X射线晶体学和电喷雾质谱对配合物进行了表征。配合物2显示适度的二次谐波产生（SHG）活性。
Six new copper(I) complexes [Cu2(L)2(H2O)](ClO4)2 (1), [Cu3(L)2(CH3CN)3(ClO4)3] (2), [Cu2(L)2Cl]ClO4·(9/4)H2O·(3/4)CH3CN (3), [Cu2(L)2(CH3CN)2](ClO4)2·2H2O (4), [Cu2(L)Br2] (5) and [Cu4(L)2Br4]·2CH3CN (6) [L = 1,3,5-tris(2-oxazolinyl)benzene] were prepared by reactions of ligand L with Cu(I) salts. Complexes 1 and 2 obtained by using the same reactants, but different solvents have 1D chain and trinuclear propeller-shaped M3L2 cage-like structures, respectively. While 3 and 4 with 2D (42·62·82)(4·62)(4·62) topological network and M2L2 macrocyclic ring structures were synthesized by addition of CuCl and CuBr, respectively. Complexes 5 and 6 with different structures were isolated by changing the metal-to-ligand ratios. 5 is an infinite 1D chain while 6 is a 3D framework with (4·122)2(42·124) topology. The results suggest that the reaction solvents, counter anions and metal-to-ligand ratios play important roles in the formation of frameworks. The complexes were characterized by X-ray crystallography and electrospray mass spectrometry. Complex 2 shows modest second harmonic generation (SHG) activity.