本文選題：Cu(I)配合物　切入點：配位點　出處：《蘇州大學》2016年碩士論文　論文類型：學位論文

【摘要】：Cu(I)配位聚合物因其獨特的結構和優(yōu)良的化學和物理性質(zhì)而備受關注。影響Cu(I)配合物結構與性能的因素有很多,如有機配體種類,Cu I與有機配體的反應比例、反應溫度和溶劑等。在本學位論文中,設計合成了一系列不同配位點的吡啶吡唑吡啶配體(pyridinyl)-1H-pyrazolyl)pyridine(pypzpy)及其甲基離子化配體,分別與CuI反應得到不同結構的配合物,考察了不同配位點對配合物的結構和性質(zhì)的影響。一、(1H-pyrazolyl)pyridine與iodopyridine反應分別得到九個配體2,2'-,3,2'-,4,2'-,2,3'-,3,3'-,4,3'-,2,4'-,3,4'-,4,4'-pypzpy,它們與CuI在不同反應溫度下反應,分離得到了11種配位聚合物[{(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經(jīng)紅外、元素分析、粉末衍射等表征,其中1·MeCN、2-6和11的結構通過單晶X射線測定。配合物1包含一個[Cu(μ-I)]2的二聚單元。配合物2和5包含一個獨特的梯型鏈[Cu2(μ-I)2]n。在配合物3中,椅式結構單元[Cu2(μ-I)(μ-I)]2通過與3,2'-pypzpy配體橋連,構筑成二維網(wǎng)狀結構。在配合物4和9中,梯型鏈[Cu2(μ-I)2]n與鋸齒型鏈[Cu(μ-I)]n通過與4,2'-pypzpy或2,4'-pypzpy配體橋連,形成了一維三重鏈結構。配合物6包含兩個[CuI]單元,通過與2,3'-pypzpy配體橋連,形成二聚體結構。配合物11是由[CuI]單元與4,4'-pypzpy配體構筑的一維鏈。在紫外光激發(fā)下,1-11發(fā)出不同的熒光。配位點對配體的配位方式、[CunIn]的結構單元、配合物的結構和性質(zhì)有很大的影響。二、配體pypzpy分別與碘甲烷反應,得到一系列的單甲基離子化配體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)和雙甲基離子化配體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)。這些配體與CuI反應得到9種配合物[(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經(jīng)紅外、元素分析等表征,其中配合物12-15的結構通過單晶X-射線測定。部分配合物可以高效催化芳基硼酸與吡唑、咪唑等的偶聯(lián)反應。
[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，

本文編號：1567927