含氮雜環(huán)羧酸類配體的配合物結(jié)構(gòu)及其性能研究
發(fā)布時(shí)間：2018-11-18 08:56
【摘要】：功能配合物因具有可控的結(jié)構(gòu)及獨(dú)特的優(yōu)良性能,已在光、電、磁、生物醫(yī)學(xué)等領(lǐng)域呈現(xiàn)出潛在的應(yīng)用價(jià)值,目前化學(xué)家們研究的重點(diǎn)在于設(shè)計(jì)合成具有特定功能的配合物。經(jīng)過(guò)大量的理論研究及實(shí)驗(yàn)結(jié)果顯示,配合物的功能與其結(jié)構(gòu)有著必然的聯(lián)系,因此如何調(diào)控配合物的結(jié)構(gòu)進(jìn)而調(diào)控其功能已成為當(dāng)前配位化學(xué)家們研究的熱點(diǎn)之一。在功能配合物中,有機(jī)配體與金屬離子由于受實(shí)驗(yàn)條件等多種因素影響可形成一系列具有新穎獨(dú)特結(jié)構(gòu)及優(yōu)良性能的配合物,故選取適合的有機(jī)配體就變得至關(guān)重要。近些年來(lái),含氮雜環(huán)羧酸類配體備受關(guān)注,此類配體同時(shí)兼具了氮雜環(huán)和羧酸配體豐富多彩的配位方式和功能性,故更有利于構(gòu)筑新型的功能配合物。為了探究影響配合物結(jié)構(gòu)的主要因素及其結(jié)構(gòu)與功能之間的相互關(guān)系,本文設(shè)計(jì)合成了一類結(jié)構(gòu)各異的含氮雜環(huán)羧酸類配體,通過(guò)將其與不同的金屬離子配位,構(gòu)筑了8個(gè)具有新穎結(jié)構(gòu)的功能配合物,分別為:Cu(DPPA)Cl(1),Mn(H2IDC)2(H2O)2(2),Cu2(TMBA)4(CH3OH)2(3),Mn(CPBm)2(H2O)4(4),Ni(CPBm)2(CH3OH)2(5),Co(CPBm)2(6)(7),Ni(CPBm)2(8),并利用X-射線單晶衍射表征了它們的結(jié)構(gòu)。其中配合物(1)為單核結(jié)構(gòu);配合物(2)為氫鍵構(gòu)筑的三維網(wǎng)絡(luò);配合物(3)中的雙核結(jié)構(gòu)單元通過(guò)氫鍵連接,形成了一維的鏈狀結(jié)構(gòu);配合物(4)通過(guò)4個(gè)不同方向的氫鍵連接形成了三維氫鍵網(wǎng)絡(luò);配合物(5)是具有44拓?fù)渚W(wǎng)絡(luò)的二維層狀結(jié)構(gòu),每個(gè)二維層相互平行堆積又構(gòu)成三維網(wǎng)絡(luò)結(jié)構(gòu);配合物(6)(7)(8)具有相似的二維層狀結(jié)構(gòu)及一維孔道結(jié)構(gòu)。此外,利用X-射線粉末衍射(PXRD)和熱重分析法(TGA)對(duì)所得配合物的相純度和熱穩(wěn)定性進(jìn)行了測(cè)試,同時(shí)對(duì)部分配合物進(jìn)行了熒光、氣體吸附和電化學(xué)儲(chǔ)鋰性能的研究。研究結(jié)果顯示,配合物(1)在303nm激發(fā)下,在363nm處有一個(gè)較強(qiáng)的熒光發(fā)射峰;配合物(7)屬于介孔材料,BET比表面積和Langmuir比表面積分別為34.42m2/g和73.62m2/g,另外,配合物(7)作為鋰離子電池的負(fù)極材料具有優(yōu)異的倍率性能和循環(huán)穩(wěn)定性能,有望成為一種新型的鋰離子電池電極材料。
[Abstract]:Functional complexes have shown potential applications in light, electricity, magnetism, biomedicine and other fields because of their controllable structure and unique excellent properties. At present, the focus of chemists is to design and synthesize complexes with specific functions. A large number of theoretical studies and experimental results show that the functions of the complexes have an inevitable relationship with their structures. Therefore, how to regulate the structure of complexes and then their functions has become one of the hot topics of coordination chemists. In the functional complexes, organic ligands and metal ions can form a series of complexes with novel and unique structures and excellent properties because of the influence of experimental conditions, so it is very important to select suitable organic ligands. In recent years, nitrogen-containing heterocyclic carboxylic acid ligands have attracted much attention. These ligands have both rich and colorful coordination modes and functions of nitrogen heterocyclic and carboxylic acid ligands, so they are more conducive to the construction of new functional complexes. In order to investigate the main factors affecting the structure of the complexes and the relationship between their structure and function, a class of heterocyclic carboxylic acid ligands with different structures were designed and synthesized, which were coordinated with different metal ions. Eight novel functional complexes,: Cu (DPPA) Cl (_ 1), Mn (H2IDC) _ 2 (H _ 2O) _ 2 (2), Cu2 (TMBA) _ 4 (CH3OH) _ 2 (3), Mn (CPBm) _ 2 (H _ 2O) _ 4 (4), were constructed. Ni (CPBm) _ 2 (CH3OH) _ 2 (5), Co (CPBm) _ 2 (6) (7), Ni (CPBm) _ 2 (8) were characterized by X-ray single crystal diffraction. The complex (1) is a mononuclear structure, the complex (2) is a three-dimensional network constructed by hydrogen bonds, and the binuclear structure units in the complex (3) are connected by hydrogen bonds to form a one-dimensional chain structure. The complex (4) forms a three-dimensional hydrogen bond network through four hydrogen bonds in different directions, and the complex (5) is a two-dimensional layered structure with 44 topological networks, each of which is stacked in parallel with each other to form a three-dimensional network structure. Complex (6) (7) (8) has similar two-dimensional layered structure and one-dimensional pore structure. In addition, the phase purity and thermal stability of the complexes were tested by X-ray powder diffraction (PXRD) and thermogravimetric analysis (TGA). The fluorescence, gas adsorption and electrochemical lithium-storage properties of some complexes were also studied. The results show that complex (1) has a strong fluorescence emission peak at 363nm under the excitation of 303nm; Complexes (7) belong to mesoporous materials, the specific surface area of BET and Langmuir are 34.42m2/g and 73.62 m2 / g, respectively. In addition, the complex (7) has excellent rate performance and cyclic stability as anode materials for lithium ion batteries. It is expected to be a new electrode material for lithium ion batteries.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O641.4
，
本文編號(hào)：2339546
[Abstract]:Functional complexes have shown potential applications in light, electricity, magnetism, biomedicine and other fields because of their controllable structure and unique excellent properties. At present, the focus of chemists is to design and synthesize complexes with specific functions. A large number of theoretical studies and experimental results show that the functions of the complexes have an inevitable relationship with their structures. Therefore, how to regulate the structure of complexes and then their functions has become one of the hot topics of coordination chemists. In the functional complexes, organic ligands and metal ions can form a series of complexes with novel and unique structures and excellent properties because of the influence of experimental conditions, so it is very important to select suitable organic ligands. In recent years, nitrogen-containing heterocyclic carboxylic acid ligands have attracted much attention. These ligands have both rich and colorful coordination modes and functions of nitrogen heterocyclic and carboxylic acid ligands, so they are more conducive to the construction of new functional complexes. In order to investigate the main factors affecting the structure of the complexes and the relationship between their structure and function, a class of heterocyclic carboxylic acid ligands with different structures were designed and synthesized, which were coordinated with different metal ions. Eight novel functional complexes,: Cu (DPPA) Cl (_ 1), Mn (H2IDC) _ 2 (H _ 2O) _ 2 (2), Cu2 (TMBA) _ 4 (CH3OH) _ 2 (3), Mn (CPBm) _ 2 (H _ 2O) _ 4 (4), were constructed. Ni (CPBm) _ 2 (CH3OH) _ 2 (5), Co (CPBm) _ 2 (6) (7), Ni (CPBm) _ 2 (8) were characterized by X-ray single crystal diffraction. The complex (1) is a mononuclear structure, the complex (2) is a three-dimensional network constructed by hydrogen bonds, and the binuclear structure units in the complex (3) are connected by hydrogen bonds to form a one-dimensional chain structure. The complex (4) forms a three-dimensional hydrogen bond network through four hydrogen bonds in different directions, and the complex (5) is a two-dimensional layered structure with 44 topological networks, each of which is stacked in parallel with each other to form a three-dimensional network structure. Complex (6) (7) (8) has similar two-dimensional layered structure and one-dimensional pore structure. In addition, the phase purity and thermal stability of the complexes were tested by X-ray powder diffraction (PXRD) and thermogravimetric analysis (TGA). The fluorescence, gas adsorption and electrochemical lithium-storage properties of some complexes were also studied. The results show that complex (1) has a strong fluorescence emission peak at 363nm under the excitation of 303nm; Complexes (7) belong to mesoporous materials, the specific surface area of BET and Langmuir are 34.42m2/g and 73.62 m2 / g, respectively. In addition, the complex (7) has excellent rate performance and cyclic stability as anode materials for lithium ion batteries. It is expected to be a new electrode material for lithium ion batteries.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O641.4
，
本文編號(hào)：2339546
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