本文選題：2 + 4(2��； 參考：《長(zhǎng)春工業(yè)大學(xué)》2017年碩士論文

【摘要】：金屬-多羧酸配體的配位化合物結(jié)構(gòu)新穎獨(dú)特、變化多端,其次,它的潛在應(yīng)用研究?jī)r(jià)值廣泛巨大,比如吸附,磁性,熒光,電化學(xué),催化等;除此之外,多羧酸配體的配位方式較之其他配體多種多樣,配位能力也強(qiáng)很多,很容易配位組裝出具有新穎獨(dú)特結(jié)構(gòu)和特異功能的配位化合物。因此這一類配合物的設(shè)計(jì)合成構(gòu)筑和性質(zhì)的研究長(zhǎng)期受到研究人員的廣泛關(guān)注。多金屬氧酸鹽作為一種綜合方面都比較優(yōu)異的無(wú)機(jī)金屬氧簇,與有機(jī)配體結(jié)合雜化形成配合物時(shí)會(huì)有很多意外的驚喜作用,以多金屬氧酸鹽為基能夠構(gòu)筑一類結(jié)構(gòu)新穎特異和潛在性能優(yōu)異的化合物。近些年來(lái),隨著配位化合物的研究與深入,金屬-有機(jī)配位聚合物的設(shè)計(jì)合成隨著聚合物(離子熱法、水熱法和溶劑熱等)合成方法的普遍應(yīng)用,設(shè)計(jì)的合理性和實(shí)際應(yīng)用性正在逐步的提高。本篇論文通過(guò)以Zn(II)為中心離子,2,4-二苯甲�；g苯二甲酸和2,5-二苯甲酰基對(duì)苯二甲酸為主配體,引入不同的含氮配體,在不同的反應(yīng)條件下,設(shè)計(jì)合成了2個(gè)結(jié)構(gòu)獨(dú)特的金屬-有機(jī)配位聚合物,并對(duì)配合物進(jìn)行了晶體結(jié)構(gòu)分析,元素分析,IR表征和TGA分析,并對(duì)熒光進(jìn)行了研究,結(jié)果如下:1、以2,4-二苯甲�；g苯二甲酸(H_2L~1),2,5-二苯甲酰基對(duì)苯二甲酸(H2L2)為主配體,選擇柔性含氮配體1,3-雙(1,2,4-三唑-1-甲基)苯為輔助配體(1,3-bis(1,2,4-triazol-1-ylmethyl)benzene),與過(guò)渡金屬Zn(II)在水熱條件下構(gòu)筑了配合物1。[Zn_2L~1L~2(mbtz)]·H_2O(1)配合物1中,四個(gè)羧基通過(guò)雙齒配位橋連兩個(gè)相鄰的Zn(II)形成了一個(gè)輪漿狀的[Zn2(CO2)4]建筑單元,配體L1連接兩個(gè)相鄰的[Zn2(CO2)4]建筑單元構(gòu)筑了1D鏈狀結(jié)構(gòu)。配體L2連接相鄰的1D鏈形成2D的層狀結(jié)構(gòu),線性含氮配體mbtz把二維層進(jìn)一步擴(kuò)展為3D具有6連接的pcu拓?fù)浣Y(jié)構(gòu)。2、以2,4-二苯甲酰基間苯二甲酸(H_2L~1),2,5-二苯甲�；鶎�(duì)苯二甲酸(H2L2)為主配體,引入新的含氮配體1,3-雙(1,2,4-三唑)丙烷為輔助配體,(1,3-bis(1,2,4-triazol-1-yl)propane),通過(guò)改變反應(yīng)條件與過(guò)渡金屬Zn(II)在水熱條件下構(gòu)筑了配合物2。[Zn_4L_2~1L_2~2(btp)_2]·7H_2O(2)配合物2與1結(jié)構(gòu)非常相似,也是以雙核的[Zn2(CO2)4]SBU為6連接點(diǎn),配體L1,L2,btp為線性連接器構(gòu)成了三維的pcu拓?fù)浣Y(jié)構(gòu)。3、以2,5-二苯甲�；鶎�(duì)苯二甲酸(H2L2)為主配體,水熱條件下與稀土金屬Dy(Ⅲ)構(gòu)筑了配合物3。[Dy(L2)1.5(H2O)2]·2H2O](3)。在3中,雙核[Dy2O4(CO2)6]建筑單元為結(jié)點(diǎn),由L2配體為連接器構(gòu)筑了三維pcu拓?fù)浣Y(jié)構(gòu),拓?fù)浞?hào)為412·63。并對(duì)化合物3的熱穩(wěn)定性和熒光性質(zhì)進(jìn)行了研究。4、以Wells-Dawson類型的磷鎢酸鹽為主配體,鄰菲羅啉(phen)為輔助配體與過(guò)渡金屬CuII和在水熱條件下合成了化合物4,[Cu(phen)2(H2O)]2+陽(yáng)離子與[Cu2(phen)3(H2O)3(P2W18O62)]2-陰離子通過(guò)π-π作用構(gòu)筑了1D鏈,相鄰的1D鏈通過(guò)O-H···O分子間作用力拓展為3D超分子結(jié)構(gòu)。此外我們還研究了化合物4的光催化性能。[Cu2(phen)3(H2O)3(P2W18O62)][Cu(phen)2(H2O)]·5H2O(4)。
[Abstract]:The coordination compounds of metal polycarboxylic ligands are novel and unique, and then the potential applications of it are widely used, such as adsorption, magnetism, fluorescence, electrochemistry, catalysis, etc. Besides, the coordination of polycarboxylic ligands is more diverse and more complex than other ligands, and is easy to be assembled. A new unique structure and specific functional coordination compounds. Therefore, the research on the design, synthesis and properties of this kind of complexes has long been concerned by researchers. Polyoxometalate is an excellent inorganic metal oxygen cluster in a comprehensive way. There are many accidents when the complexes are combined with organic ligands to form complexes. In recent years, the design and synthesis of metal organic coordination polymers have been designed and synthesized with the general application of the synthetic methods of polymer (ionic calorimetry, hydrothermal method and solvent heat etc.). By taking Zn (II) as the central ion, 2,4- two benzoyl benzoyl two formic acid and 2,5- two benzoyl terephthalic terephthalic acid as the main ligands, this paper has designed and synthesized 2 unique metal organic coordination polymers in different reaction conditions. The crystal structure analysis, elemental analysis, IR characterization and TGA analysis were carried out and the fluorescence was studied. The results are as follows: 1, 2,4- two benzoyl benzene two formic acid (H_2L~1), 2,5- two benzoyl terephthalic acid (H2L2) as the main ligand, 1,3- double (1,2,4- three azole -1- methyl) benzene as the auxiliary ligand (1,3-bis, 1,3-bis) as the auxiliary ligand (1,3-bis) as the auxiliary ligand (1,3-bis) as the auxiliary ligand (1,3-bis, 1,3-bis) as the auxiliary ligand (1,3-bis). (1,2,4-triazol-1-ylmethyl) benzene), with the transition metal Zn (II) constructed in the hydrothermal condition, the complex 1.[Zn_2L~1L~2 (mbtz)]. H_2O (1) complex 1, the four carboxyl groups formed a pulley like [Zn2 (CO2) 4] building unit through the double tooth distribution bridge and two adjacent Zn (II), and the ligands connected two adjacent building units. 1D chain structure is constructed. Ligand L2 connects adjacent 1D chains to form a layered structure of 2D, and linear nitrogen ligand mbtz extends the two-dimensional layer to 3D with 6 connected PCU topological structure.2, with 2,4- two benzoyl benzoyl benzoic acid (H_2L~1), 2,5- two benzoyl terephthalic terephthalic acid (H2L2) and new nitrogen ligand. Three azole) propane is an auxiliary ligand, (1,3-bis (1,2,4-triazol-1-yl) propane). By altering the reaction conditions and the transition metal Zn (II), the complex 2.[Zn_4L_2~1L_2~2 (BTP) _2]. 7H_2O (2) complex is constructed very similar to the structure of the complex 2 and 1, and the dual nucleus [Zn2 (CO2) 4]SBU is the 6 connection point. A three-dimensional PCU topology.3 is formed, with 2,5- two benzoyl terephthalic acid (H2L2) as the main ligand and 3.[Dy (L2) 1.5 (H2O) 2] 2H2O] (3) complex with rare earth metal Dy (III) under hydrothermal conditions. In 3, the dual core [Dy2O4 (CO2) building unit is a node, and a three-dimensional topological structure is constructed by the ligands, with a topological symbol of 412. 63 The thermal stability and fluorescence properties of compound 3 were studied by.4, with Wells-Dawson type phosphotungstate as the main ligand, adjacent phenanthroline (phen) as the auxiliary ligand and transition metal CuII and synthesis of compound 4, [Cu (phen) 2 (H2O)]2+ cations and [Cu2 (phen) 3 (H2O) 3 (P2W18O62) anion through the pion - pi In the 1D chain, the adjacent 1D chain was extended to 3D supramolecular structure through the intermolecular force of O-H. O. In addition, we also studied the photocatalytic properties of compound 4,.[Cu2 (phen) 3 (H2O) 3 (P2W18O62)][Cu (phen) 2 (H2O)].
【學(xué)位授予單位】：長(zhǎng)春工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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本文編號(hào)：1972610