刚性芳香羧酸类配合物的自组装、结构及性能研究

发布时间：2018-06-07 10:26

本文选题：配合物 + 2　；参考：《中北大学》2017年硕士论文

【摘要】：近年来,由于刚性芳香羧酸类配体构筑的配合物在微孔吸附、催化剂、材料以及光、电、磁学等方面显示了超强的优越性,因此,对刚性芳香羧酸类配合物的研究意义重大。基于此本文选择2,6-萘二甲酸二甲酯(NDADE)和3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作为有机配体,通过与不同金属离子进行配位,成功构筑了10个新颖结构的配合物,并对其进行了单晶X-射线衍射、元素分析、红外光谱、热重、粉末X-射线衍射等一系列表征,同时,对部分配合物进行了荧光性能检测。主要内容如下:(1)选用2,6-萘二甲酸二甲酯(NDADE)作为有机配体,以过渡金属Zn~(2+)、Cd~(2+)作为金属离子,通过原位水解反应,构筑两个新颖结构的配合物[M(NDAME)_2H_2O]∞(M=Zn~(2+),1;M=Cd~(2+),2)。在配合物1中,每个NDAME配体通过μ2-η1:η1配位模式与两个Zn~(2+)进行配位形成1D链结构,其中,羧基氧原子和Zn~(2+)离子连接形成一个扭曲的8-元环。在配合物2中,每个NDAME配体通过μ2-η1:η2配位模式与Cd~(2+)中心离子桥联形成1D链结构,其中,Cd~(2+)中心离子与羧基氧原子相连形成一个无机Cd-O链。在固态和各种溶剂分散液中,研究了配合物1和2的荧光性质,结果表明,配合物1和2对NB(硝基苯)和2-NT(2-硝基甲苯)以及Cu~(2+)和Fe3+离子具有高度的选择性和灵敏性,因此,它们可作为肉眼比色检测小分子和金属离子的荧光探针。同时,还详细研究了它们的猝灭机理。(2)选用3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作为有机配体,以Co~(2+)、Ni~(2+)、Cu~(2+)、Pb~(2+)作为配位金属离子,通过溶剂热反应,构筑了四个结构各异的配合物{[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,每两个cpcpa2-配体采用μ2-κN,O:κO′配位模式与两个Co~(2+)中心离子进行配位形成一个双核配合物,相邻双核之间再通过氢键O-H···O相互作用形成一个2D超分子层结构。在配合物4中,每个cpcpa2-配体采用μ1-κN,O配位模式与一个Ni~(2+)中心离子进行配位形成一个单核配合物,相邻单核之间再通过氢键O-H···O连接形成一个2D超分子层结构。在配合物5中,μ3-O6原子桥联相邻Cu_4O_4次级结构单元形成1D链状结构,相邻1D链通过cpcpa2-配体采用μ3-κN,O:κO′:κO′′的配位模式形成2D层状结构,相邻2D层状结构之间进一步通过O-H···O氢键相互作用形成一个3D超分子结构。在配合物6中,相邻Pb3次级结构单元通过cpcpa2-配体羧基氧原子形成1D链状结构,相邻1D链进一步通过cpcpa2-配体采用μ6-κN,O:κO:κO′:κO′′:κO′′:κO′′′和μ5-κN,O:κO:κO′:κO′′,O′′′:κO′′′两种不同配位模式形成3D金属-有机骨架。同时,对配合物6的荧光性质进行了研究。(3)选用3-4-(羧基苯基)-6-羧基吡啶(H2cpcpa)作为有机配体,以稀土离子Eu~(3+)、Ce~(3+)、Pr~(3+)以及Nd~(3+)作为配位金属中心,通过溶剂热反应,构筑四个同构配合物[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,相邻双核次级结构单元Ln_2O_3通过配体采用μ3-κN,O:κO:κO′的配位模式连接形成1D链状结构,相邻1D链进一步通过氢键相互作用形成2D超分子结构。同时,对配合物7的荧光性质进行了研究。
[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.
【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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