本文選題：配位聚合物 + 金屬-有機(jī)骨架��； 參考：《西北大學(xué)》2015年博士論文

【摘要】：配位聚合物(CPs)及金屬-有機(jī)骨架化合物(MOFs)是指以金屬離子或其簇作為節(jié)點,有機(jī)多齒橋聯(lián)配體為連桿自組裝形成的具有周期性網(wǎng)絡(luò)結(jié)構(gòu)的低密度晶態(tài)材料。因其層出不窮的結(jié)構(gòu)和潛在的應(yīng)用價值而備受關(guān)注。特別是MOFs作為新一代超低密度和孔結(jié)構(gòu)高度有序多孔材料,由于其通常具有結(jié)構(gòu)多樣、溶解度低、孔徑大小與形狀及表面性質(zhì)可調(diào)等特點,在過去二十年間得到迅猛發(fā)展,成為材料和化學(xué)領(lǐng)域的研究熱點之一。有序的結(jié)構(gòu)特征也使得其尤為適合用來研究結(jié)構(gòu)-性能關(guān)系。盡管目前各種各樣的CPs和MOFs被人們不斷地合成出來,但設(shè)計合成有特定結(jié)構(gòu)和性能的CPs和MOFs化合物仍然是非常具有挑戰(zhàn)性的工作。這是因為它們的結(jié)構(gòu)和性能不僅與其構(gòu)筑基元即有機(jī)配體和金屬離子有關(guān),而且還往往受到各種合成條件的影響。因此除了精心設(shè)計有機(jī)配體外,研究這些條件對化合物結(jié)構(gòu)的影響是非常必要的。目前,相對于苯環(huán)芳香多羧酸配體而言,功能化的氮雜環(huán)羧酸配體目前研究相對較少,基于以上考慮,本論文在配位化學(xué)、超分子化學(xué)及晶體工程的原理下,選用不同基團(tuán)功能化、大小和形狀也不同的有機(jī)配體來構(gòu)筑CPs/MOFs,主要研究配體大小,剛?cè)嵝?功能化基團(tuán)及配體的齒數(shù)和角度等對配合物結(jié)構(gòu)和性質(zhì)的影響。第一章,通過調(diào)節(jié)反應(yīng)條件,利用甲基功能化的V型半剛性配體4-(2-甲基-1-咪唑基亞甲基)苯甲酸(HL1)在水熱條件下與不同過渡金屬鹽反應(yīng)合成了5例CPs,它們分別是：[Zn(L1)2]n(1)、{[Zn(L1)2]·(H2O)}n(2)、{[Cd(L1)2]-(H2O)}n(3)、{[Co(L1)2]·(H2O)2}n (4)、[Cu(L1)2]n(5)。單晶結(jié)構(gòu)測試表明1和2中都含有單手性的2D螺旋層,不同的是1中兩個同手性的螺旋層相互貫穿形成2D→2D的平行穿插結(jié)構(gòu),整個單晶結(jié)構(gòu)是單手性的,但固體樣品的圓二色譜測試表明其是外消旋混合物。而2的結(jié)構(gòu)中則含有兩種不同手性的2D螺旋層,它們堆積形成內(nèi)消旋產(chǎn)物。2和3是同構(gòu)的,4和5則是不同形式的1D串珠鏈結(jié)構(gòu)。主要研究了化合物1對過渡金屬離子和溶劑分子的熒光識別性能；實驗結(jié)果表明其可以在水相中高選擇性識別Cu2+離子；對于有機(jī)溶劑則可以專一的識別硝基苯類分子。第二章,我們選用目前較少被研究的2-氟異煙酸(HL2)和5-氟煙酸(HL3)在不同條件下與多種金屬鹽和氮雜環(huán)輔助配體合成了8個具有不同結(jié)構(gòu)特征的過渡金屬配合物。它們的結(jié)構(gòu)簡式分別為：[Cd(L2)2(bpe)]n (6)、[Ag(L2)]n (7)、{[Cu(L3)2(H2O)]-H2O}n (8)、[Cu(L3)2]n (9)、[Cu2(L3)4(bpy)(H2O)2]n (10)、[Co(L3)2 (H2O)4]n(11)、[Co(L3)2(bpe)]n(12)和[Co(L3)2(bpp)2(H2O)]n (13)。其中6和12是相似的一維梯子鏈結(jié)構(gòu),7是1D直線鏈結(jié)構(gòu),8和9是3D骨架結(jié)構(gòu),10是2D波浪型網(wǎng)格結(jié)構(gòu),11是一個單核化合物,而13則是1D折線型單鏈結(jié)構(gòu)。分別表征了它們的粉末X-射線衍射(XRD)、紅外光譜、熱重等性質(zhì)；對6和7進(jìn)行了室溫固態(tài)熒光光譜研究；對9和12則測試了其變溫磁學(xué)性質(zhì)。在第三章中,利用剛性含毗啶基團(tuán)(路易斯堿性)作為活性基團(tuán)的角形四羧酸配體2,6-吡啶-5,5'-二(間苯二甲酸)(H4L4)作為連接體構(gòu)筑單元,在水熱條件下利用其與過渡金屬離子(Zn2+、Mn2+)成功合成兩例具有(3,4,6)連接的拓?fù)漕愋蜑閠wf-d的籠狀納米孔洞結(jié)構(gòu)的MOFs化合物,即：{[Zn2(L4) (H2O)1.5]·(xGUEST)}n(14)和 {[H2N(CH3)2]0.25[Mn3.75 (L4)1.5(Cl)0.75(HCOO)(DMF) (H20)0.675]·(xGUEST)}n(15)。結(jié)構(gòu)分析表明它們的結(jié)構(gòu)中均含有兩種或多種無機(jī)SBU(包括罕見的聯(lián)輪槳SBU)和孔徑大小不同的空穴,即通過控制多個羧基配位基團(tuán)在配體中的分布成功實現(xiàn)了多個次級構(gòu)筑單元組裝的異質(zhì)性即復(fù)雜多樣性MOFs。化合物14的熒光測試表明其在固態(tài)和溶劑中表現(xiàn)出不同機(jī)理的發(fā)光行為；氣體吸附實驗表明它們均對CO2氣體具有選擇性。
[Abstract]:Coordination polymers (CPs) and metal organic framework compounds (MOFs) are low density crystalline materials with periodic network structures formed by metal ions or their clusters as nodes and organic multi tooth bridging ligands self assembled for connecting rods. Because of their endless structure and potential value, MOFs is a new generation. Highly ordered porous materials with ultra-low density and pore structure have been developed rapidly in the past twenty years because of their characteristics of diverse structure, low solubility, pore size, shape and surface properties, which have become one of the hot topics in the field of materials and chemistry. Structure and performance relationships. Although a variety of CPs and MOFs are constantly being synthesized, it is still a very challenging task to design and synthesize CPs and MOFs compounds with specific structures and properties. This is because their structure and properties are not only related to the structural elements that are organic ligands and metal ions, but also often Therefore, it is necessary to study the effects of these conditions on the structure of the compounds in addition to the careful design of organic compounds in vitro. At present, the functionalized nitrogen heterocyclic carboxylic ligands are relatively less studied than the phenyl aromatic polycarboxylic ligands. Based on the above consideration, this paper is in coordination chemistry and supramolecular. Under the principle of chemical and crystal engineering, CPs/MOFs is constructed by using different functional groups, size and shape of organic ligands. The effects of ligand size, stiffness, function group and tooth number and angle on the structure and properties of the complex are mainly studied. Chapter 1, by adjusting the reaction conditions, using the methylation V type The semirigid ligand 4- (2- methyl -1- imidazolyl) benzoic acid (HL1) synthesized 5 cases of CPs with different transition metal salts under hydrothermal conditions. They are [Zn (L1) 2]n (1), {[Zn (L1) 2] (2), 4, 5. Single crystal structure tests show that 1 and 2 contain mono chiral The spiral layer, which is different in that 1 of the two helix layers of the 1 chiral helix penetrate into the parallel interpenetrating structure of the 2D, and the whole single crystal structure is mono chiral, but the round two chromatographic test of the solid sample indicates that it is a raceme mixture. The structure of the 2 contains two different chiral 2D helix layers, which accumulate to form internal raceme products.2 and 3. It is isomorphic, 4 and 5 are different forms of 1D string structure. The fluorescence recognition performance of compound 1 for transition metal ions and solvent molecules is mainly studied. The experimental results show that it can identify Cu2+ ions high selectively in the water phase; for organic solvents, we can identify nitrobenzene molecules in a special way. Chapter second, we choose the order. The less studied 2- fluoro nicotinic acid (HL2) and 5- fluoric acid (HL3) synthesized 8 transition metal complexes with various metal salts and nitrogen heterocyclic auxiliary ligands under different conditions. Their structure simple forms are [Cd (L2) 2 (BPE)]n (6), [Ag (L2)]n (7), {[Cu (9), 4 (9) 4). Bpy) (H2O) 2]n (10), [Co (L3) 2 (H2O) 4]n (11), [Co (L3) 2 (BPE)]n (12) and [Co (13) 2 (13). Of which 6 and 12 are similar one-dimensional ladder chain structures, 7 are linear chain structures, 8 and 9 are skeleton structures, 10 are wavy grid structures, and are a single core compound. Final X- ray diffraction (XRD), infrared spectrum, thermogravimetry, and other properties; 6 and 7 were studied at room temperature by solid-state fluorescence; the temperature magnetic properties were tested for 9 and 12. In the third chapter, the angular four carboxylic acid ligand, 2,6- pyridine -5,5'- two (H4L4) (H4L4), as the active group, was used as the active group. In the hydrothermal condition, two cases of MOFs compounds with caged nanopore structure of (3,4,6) connection twf-d are successfully synthesized under hydrothermal conditions, namely, {[Zn2 (H2O) 1.5] (xGUEST)}n (14) and 1.5 (H2O) 0.75. ST)}n (15). Structural analysis shows that their structures contain two or more inorganic SBU (including rare wheel propeller SBU) and holes with different aperture sizes, that is, by controlling the distribution of multiple carboxylic ligands in the ligand, the heterogeneity of multiple secondary architecture units is successfully realized, namely, the fluorescence of complex diversity MOFs. compound 14 The results show that they exhibit different mechanisms of luminescence in solid state and solvent. Gas adsorption experiments show that they all have selectivity for CO2 gas.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：O641.4

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相關(guān)期刊論文 前2條

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2 姜寧;鄧志勇;王公應(yīng);劉紹英;;金屬有機(jī)框架材料的制備及在吸附分離CO_2中的應(yīng)用[J];化學(xué)進(jìn)展;2014年10期

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本文編號：1902728