CuI与吡啶吡唑吡啶类配体的自组装

发布时间：2018-03-05 00:15

  本文选题：Cu(I)配合物　切入点：配位点　出处：《苏州大学》2016年硕士论文　论文类型：学位论文

【摘要】：Cu(I)配位聚合物因其独特的结构和优良的化学和物理性质而备受关注。影响Cu(I)配合物结构与性能的因素有很多,如有机配体种类,Cu I与有机配体的反应比例、反应温度和溶剂等。在本学位论文中,设计合成了一系列不同配位点的吡啶吡唑吡啶配体(pyridinyl)-1H-pyrazolyl)pyridine(pypzpy)及其甲基离子化配体,分别与CuI反应得到不同结构的配合物,考察了不同配位点对配合物的结构和性质的影响。一、(1H-pyrazolyl)pyridine与iodopyridine反应分别得到九个配体2,2'-,3,2'-,4,2'-,2,3'-,3,3'-,4,3'-,2,4'-,3,4'-,4,4'-pypzpy,它们与CuI在不同反应温度下反应,分离得到了11种配位聚合物[{(2,2'-pypzpy)Cu}(?-I)]2(1),[{Cu3(μ3-I)3}(μ-3,2'-pypzpy)]n(2),[{Cu2(μ-I)(μ3-I)}2(3,2'-pypzpy)2]n(3),[{Cu(μ3-I)}2(4,2'-pypzpy)2{Cu(μ-I)}2]n(4),[{Cu3(μ3-I)3}(μ-2,3'-pypzpy)]n(5),[(Cu I)(μ-2,3'-pypzpy)]2(6),[(Cu2I2)(3,3'-pypzpy)](7),[(CuI)(4,3'-pypzpy)](8),[{Cu(μ3-I)}2(μ-2,4'-pypzpy)2{Cu(μ-I)}2]n(9),[(Cu I)(3,4'-pypzpy)](10)和[(Cu I)(μ-4,4'-pypzpy)]n(11)。配合物1-11经红外、元素分析、粉末衍射等表征,其中1·MeCN、2-6和11的结构通过单晶X射线测定。配合物1包含一个[Cu(μ-I)]2的二聚单元。配合物2和5包含一个独特的梯型链[Cu2(μ-I)2]n。在配合物3中,椅式结构单元[Cu2(μ-I)(μ-I)]2通过与3,2'-pypzpy配体桥连,构筑成二维网状结构。在配合物4和9中,梯型链[Cu2(μ-I)2]n与锯齿型链[Cu(μ-I)]n通过与4,2'-pypzpy或2,4'-pypzpy配体桥连,形成了一维三重链结构。配合物6包含两个[CuI]单元,通过与2,3'-pypzpy配体桥连,形成二聚体结构。配合物11是由[CuI]单元与4,4'-pypzpy配体构筑的一维链。在紫外光激发下,1-11发出不同的荧光。配位点对配体的配位方式、[CunIn]的结构单元、配合物的结构和性质有很大的影响。二、配体pypzpy分别与碘甲烷反应,得到一系列的单甲基离子化配体1-methyl-3-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide([3,2'-pypzpym]I),1-methyl-4-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide([4,2'-pypzpym]I),1-methyl-4-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide([2,4'-pypzpym]I),1-methyl-3-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide([2,3'-pypzpym]I)和双甲基离子化配体1-methyl-3-(1-(1-methylpyridin-1-ium-4-yl)-1H-pyrazol-3-yl)pyridin-1-ium diiodide([3,4'-pypzpydm]I2),4,4'-(1H-pyrazole-1,3-diyl)bis(1-methylpyridin-1-ium)diiodide([4,4'-pypzpydm]I2),3,3'-(1H-pyrazole-1,3-diyl)bis(1-methylpyridin-1-ium)diiodide([3,3'-pypzpydm]I2),1-methyl-3-(3-(1-methylpyridin-1-ium-4-yl)-1H-pyrazol-1-yl)pyridin-1-ium diiodide([4,3'-pypzpydm]I2)。这些配体与CuI反应得到9种配合物[(CuI2)(3,2'-pypzpym)](12),[(Cu4I6)(3,2'-pypzpym)2]n(13),[(Cu4I6)(4,2'-pypzpym)2](14),[(Cu I2)(2,3'-pypzpym)](15),[(Cu I3)(3,3'-pypzpydm)](16),[(CuI3)(4,3'-pypzpydm)}](17),[(Cu I2)(2,4'-pypzpym)](18),[(Cu3I7)(3,4'-pypzpydm)2](19)和[(CuI7)(4,4'-pypzpydm)3](20)。配合物12-20经红外、元素分析等表征,其中配合物12-15的结构通过单晶X-射线测定。部分配合物可以高效催化芳基硼酸与吡唑、咪唑等的偶联反应。
[Abstract]:Cu (I) coordination polymers because of its unique structure and excellent physical and chemical properties have attracted much attention. The effect of Cu (I) there are many factors such as the structure and properties of the organic ligand, reaction ratio Cu I and organic ligands, reaction temperature and solvent. In this degree paper pyridine, pyrazole pyridine ligands a series of different coordination sites were designed and synthesized (pyridinyl) -1H-pyrazolyl) pyridine (pypzpy) and its methyl ionized ligand, respectively with the CuI reaction of complexes with different structures, the effects of different structures and properties of coordination sites of the complexes. A, (1H-pyrazolyl) pyridine and iodopyridine reaction respectively nine 3,2'-, 4,2'-, 2,2'- ligand, 2,3'-, 3,3'-, 4,3'-, 2,4'-, 3,4'-, 4,4'-pypzpy, CuI and their reaction at different reaction temperature, isolated 11 kinds of coordination polymers [{(2,2'-pypzpy) (Cu}? -I)]2 (1), [{Cu3 (3-I (3}) 渭-3,2'-pypzpy)]n(2),[{Cu2(渭-I)(渭3-I)}2(3,2'-pypzpy)2]n(3),[{Cu(渭3-I)}2(4,2'-pypzpy)2{Cu(渭-I)}2]n(4),[{Cu3(渭3-I)3}(渭-2,3'-pypzpy)]n(5),[(Cu I)(渭-2,3'-pypzpy)]2(6),[(Cu2I2)(3,3'-pypzpy)](7),[(CuI)(4,3'-pypzpy)](8),[{Cu(渭3-I)}2(渭-2,4'-pypzpy)2{Cu(渭-I)}2]n(9),[(Cu I)(3,4'-pypzpy)](10)鍜孾(Cu I)(渭-4,4'-pypzpy)]n(11).閰嶅悎鐗，

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