本文選題：配合物 + 2��； 參考：《中北大學(xué)》2017年碩士論文

【摘要】：近年來,由于剛性芳香羧酸類配體構(gòu)筑的配合物在微孔吸附、催化劑、材料以及光、電、磁學(xué)等方面顯示了超強的優(yōu)越性,因此,對剛性芳香羧酸類配合物的研究意義重大�；诖吮疚倪x擇2,6-萘二甲酸二甲酯(NDADE)和3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作為有機配體,通過與不同金屬離子進行配位,成功構(gòu)筑了10個新穎結(jié)構(gòu)的配合物,并對其進行了單晶X-射線衍射、元素分析、紅外光譜、熱重、粉末X-射線衍射等一系列表征,同時,對部分配合物進行了熒光性能檢測。主要內(nèi)容如下:(1)選用2,6-萘二甲酸二甲酯(NDADE)作為有機配體,以過渡金屬Zn~(2+)、Cd~(2+)作為金屬離子,通過原位水解反應(yīng),構(gòu)筑兩個新穎結(jié)構(gòu)的配合物[M(NDAME)_2H_2O]∞(M=Zn~(2+),1;M=Cd~(2+),2)。在配合物1中,每個NDAME配體通過μ2-η1:η1配位模式與兩個Zn~(2+)進行配位形成1D鏈結(jié)構(gòu),其中,羧基氧原子和Zn~(2+)離子連接形成一個扭曲的8-元環(huán)。在配合物2中,每個NDAME配體通過μ2-η1:η2配位模式與Cd~(2+)中心離子橋聯(lián)形成1D鏈結(jié)構(gòu),其中,Cd~(2+)中心離子與羧基氧原子相連形成一個無機Cd-O鏈。在固態(tài)和各種溶劑分散液中,研究了配合物1和2的熒光性質(zhì),結(jié)果表明,配合物1和2對NB(硝基苯)和2-NT(2-硝基甲苯)以及Cu~(2+)和Fe3+離子具有高度的選擇性和靈敏性,因此,它們可作為肉眼比色檢測小分子和金屬離子的熒光探針。同時,還詳細(xì)研究了它們的猝滅機理。(2)選用3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作為有機配體,以Co~(2+)、Ni~(2+)、Cu~(2+)、Pb~(2+)作為配位金屬離子,通過溶劑熱反應(yīng),構(gòu)筑了四個結(jié)構(gòu)各異的配合物{[Co_2(cpcpa)_2(H_2O)_8].2H_2O}n(3),{[Ni(cpcpa)(H_2O)_4].2H_2O}n(4),{[Cu_4(μ2-O)_2(μ3-O)2(cpcpa)_2(H_2O)_2].2H_2O}n(5)和[Pb_3(cpcpa)_2(NO_3)(H_2O)]n(6)。在配合物3中,每兩個cpcpa2-配體采用μ2-κN,O:κO′配位模式與兩個Co~(2+)中心離子進行配位形成一個雙核配合物,相鄰雙核之間再通過氫鍵O-H···O相互作用形成一個2D超分子層結(jié)構(gòu)。在配合物4中,每個cpcpa2-配體采用μ1-κN,O配位模式與一個Ni~(2+)中心離子進行配位形成一個單核配合物,相鄰單核之間再通過氫鍵O-H···O連接形成一個2D超分子層結(jié)構(gòu)。在配合物5中,μ3-O6原子橋聯(lián)相鄰Cu_4O_4次級結(jié)構(gòu)單元形成1D鏈狀結(jié)構(gòu),相鄰1D鏈通過cpcpa2-配體采用μ3-κN,O:κO′:κO′′的配位模式形成2D層狀結(jié)構(gòu),相鄰2D層狀結(jié)構(gòu)之間進一步通過O-H···O氫鍵相互作用形成一個3D超分子結(jié)構(gòu)。在配合物6中,相鄰Pb3次級結(jié)構(gòu)單元通過cpcpa2-配體羧基氧原子形成1D鏈狀結(jié)構(gòu),相鄰1D鏈進一步通過cpcpa2-配體采用μ6-κN,O:κO:κO′:κO′′:κO′′:κO′′′和μ5-κN,O:κO:κO′:κO′′,O′′′:κO′′′兩種不同配位模式形成3D金屬-有機骨架。同時,對配合物6的熒光性質(zhì)進行了研究。(3)選用3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作為有機配體,以稀土離子Eu~(3+)、Ce~(3+)、Pr~(3+)以及Nd~(3+)作為配位金屬中心,通過溶劑熱反應(yīng),構(gòu)筑四個同構(gòu)配合物[Ln_2(Hcpcpa)_4(cpcpa)(H_2O)_3]n(Ln=Eu(7)、Ce(8)、Pr(9)、Nd(10))。在配合物7-10中,相鄰雙核次級結(jié)構(gòu)單元Ln_2O_3通過配體采用μ3-κN,O:κO:κO′的配位模式連接形成1D鏈狀結(jié)構(gòu),相鄰1D鏈進一步通過氫鍵相互作用形成2D超分子結(jié)構(gòu)。同時,對配合物7的熒光性質(zhì)進行了研究。
[Abstract]:In recent years, the Complexes Constructed by rigid aromatic carboxylic ligands have shown great superiority in microporous adsorption, catalysts, materials, light, electricity, magnetism and so on. Therefore, the research of rigid aromatic carboxylic complexes is of great significance. Based on this paper, the 2,6- naphthalene two formic acid two methyl ester (NDADE) and 3-4- (carboxyphenyl) -6- carboxyl pyridine are selected. As an organic ligand, H2cpcpa is used as an organic ligand to coordinate with different metal ions. 10 novel complexes have been constructed successfully, and a series of characterization of single crystal X- ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetry, powder X- ray diffraction and so on, and the fluorescence detection of some complexes are carried out. The main contents are as follows: (1) select 2,6- naphthalene two formic acid two methyl ester (NDADE) as organic ligand, transition metal Zn~ (2+), Cd~ (2+) as metal ions, through in situ hydrolysis reaction, construct two novel complexes, [M (NDAME) _2H_2O] (M=Zn~ (2+), 1, M=Cd~ (2), 2). In the complex 1, each ligand is entered through the mode of micron ETA 1 coordination and two The row coordination form 1D chain structure, in which the carboxyl oxygen atom and the Zn~ (2+) ions connect to form a twisted 8- ring. In the complex 2, each NDAME ligand forms a 1D chain structure with the Cd~ (2+) center ion bridge through the 2- ETA 1: ETA 2 coordination mode, in which the Cd~ (2+) center is connected to the carboxyl oxygen atom to form an inorganic chain. In various solvent dispersions, the fluorescence properties of complexes 1 and 2 have been studied. The results show that complexes 1 and 2 have high selectivity and sensitivity for NB (nitrobenzene) and 2-NT (2- nitrotoluene) and Cu~ (2+) and Fe3+ ions. Therefore, they can be used as fluorescence probes for detecting small molecules and metal ions in the naked eye. Their quenching mechanism. (2) select 3-4- (carboxyphenyl) -6- carboxylic pyridine (H2cpcpa) as organic ligand, Co~ (2+), Ni~ (2+), Cu~ (2+), Pb~ (2+) as coordination metal ions, and build up four complexes of different structures by solvent thermal reaction. -O) 2 (cpcpa) _2 (H_2O) _2].2H_2O}n (H_2O) _2].2H_2O}n (5) and [Pb_3 (cpcpa) _2 (NO_3) (H_2O)]n (6). In the complex 3, each of the two cpcpa2- ligands is coordinated with two central ions to form a dual core complex, and the adjacent binuclear interaction forms a supramolecular layer through the interaction of hydrogen bonds. In the complex 4, each cpcpa2- ligand uses the 1- kappa N, the O coordination mode and a Ni~ (2+) center ion to form a mononuclear complex, and the adjacent mononuclear is connected by the hydrogen bond O-H. O to form a 2D supramolecular layer structure. In the complex 5, the 1D chain structure of the adjacent Cu_4O_4 secondary structure unit of the mu 3-O6 atom is formed. The adjacent 1D chain uses the ligand mode of the cpcpa2- ligand to form a 2D layered structure with the coordination mode of 3- kappa N, O: kappa O ', and a 3D supramolecular structure is formed by the interaction of O-H. O hydrogen bonds between the adjacent 2D layered structures. The adjacent 1D chains were further used to use the cpcpa2- ligand for the use of micron kappa N, O: kappa O: kappa O ', kappa O' ', kappa O', and mu 5- N, and the metal organic skeleton was formed by two different coordination modes, kappa ': kappa', ': kappa' '. Meanwhile, the fluorescence properties of the complex 6 were studied. (3) select carboxyphenyl phenyl) carboxyl carboxylic pyridine. H2cpcpa, as an organic ligand, uses rare earth ions as Eu~ (3+), Ce~ (3+), Pr~ (3+) and Nd~ (3+) as the coordination metal center, and constructs four isomorphic complexes [Ln_2 (Hcpcpa) _4 (8), 9, 10) by solvent thermal reaction. N, the coordination mode of O: kappa O: kappa O 'formed a 1D chain structure, and the adjacent 1D chain further formed a 2D supramolecular structure through hydrogen bond interaction. Meanwhile, the fluorescence properties of the complex 7 were studied.
【學(xué)位授予單位】：中北大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

【參考文獻】

相關(guān)期刊論文 前6條

1 邱曉敏;李洋;宋江鋒;周瑞莎;;2,6-萘二甲酸構(gòu)筑配合物的研究進展[J];化學(xué)通報;2016年04期

2 孔治國;郭勝男;于淼;馮斯e，

本文編號：1990845