發(fā)布時(shí)間：2018-04-14 04:32

  本文選題：多金屬氧簇 + 無(wú)機(jī)-有機(jī)雜化材料�。� 參考：《延邊大學(xué)》2017年碩士論文

【摘要】：多金屬氧酸鹽也稱多酸,是高氧化態(tài)的前過(guò)渡金屬離子通過(guò)氧連接而成的一類多金屬氧簇化合物。由于具有結(jié)構(gòu)多樣性和良好的性質(zhì),使其在諸多領(lǐng)域都展現(xiàn)出潛在的應(yīng)用價(jià)值,例如磁性、醫(yī)藥、光化學(xué)、生物催化等領(lǐng)域。多酸和多酸之間可以通過(guò)M-O-M'鍵(M,M':過(guò)渡金屬)相連。金屬有機(jī)骨架(MOFs)也被稱為多孔配位聚合物(PCPs),因其潛在可設(shè)計(jì)的拓?fù)浣Y(jié)構(gòu)和良好應(yīng)用性能得到迅速發(fā)展。作為一個(gè)新型多孔材料,它的合成可以通過(guò)配位鍵連接金屬節(jié)點(diǎn)(離子或集群)和有機(jī)橋連配體。由于結(jié)構(gòu)和功能的可調(diào)性,使其在合成化學(xué)和材料科學(xué)領(lǐng)域中飛速發(fā)展。多酸可以作為重要的無(wú)機(jī)構(gòu)筑單元與有機(jī)配體或金屬有機(jī)配體相連合成新的有機(jī)-無(wú)機(jī)雜化化合物。有時(shí)這種多酸基配位聚合物被稱為POMOFs。多酸基配位聚合物的研究已成為多酸化學(xué)發(fā)展的一個(gè)研究熱門。本文以Zn-ε-Keggin為構(gòu)筑單元,以二齒半剛性配體4'-(4-carboxyphenoxy)-[1,1'-biphenyl]-4-carboxylie(CPBPC)和三齒半剛性配體4,4',4"-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoic acid)(TATAB)為橋聯(lián)配體在水熱條件下與氯化鋅反應(yīng)生成兩例基于多酸的無(wú)機(jī)-有機(jī)雜化化合物。在合成過(guò)程中通過(guò)調(diào)節(jié)反應(yīng)條件,例如溶液的pH值、反應(yīng)溫度和原料配比等,找到制備目標(biāo)化合物的最佳反應(yīng)條件,并對(duì)其性質(zhì)進(jìn)行表征。本文合成的化合物分別為:[TBA]3[PMov8MoⅥ4O36(OH)4Zn4][CPBPC]2(1)[TBA]3[PMov8MoⅥ4O36(OH)4Zn4][PTABAB][HPTABAB].7H20(2)(PTABAB4,4'-((6-(phenylamino)-1,3,5-triazine-2,4-diyl)bis(azanediyl))dibenzoate)。配體TATAB在反應(yīng)過(guò)程中發(fā)生脫羧反應(yīng)生成PTABAB。在晶體1中,Zn-ε-Keggin單元與配體CPBPC生成一種具有八層互穿的three-dimensional(3D)dia骨架結(jié)構(gòu),其可以理解成由2個(gè)四層互穿單元進(jìn)一步互穿。晶體2具有two-dimensional(2D)層狀結(jié)構(gòu),相鄰層互穿形成雙層,并且相鄰的互傳層以AAA序列排列。在單配體條件下,這是首例Zn-ε-Keggin單元上的鋅離子具有兩種不同類型幾何配位的報(bào)道。同時(shí)對(duì)它們的電化學(xué)性能進(jìn)行了測(cè)試。
[Abstract]:Polyoxometalates, also known as polyacids, are a class of polyoxometallic clusters formed by oxygen bonding of highly oxidized pretransition metal ions.Due to its diverse structure and good properties, it has shown potential applications in many fields, such as magnetism, medicine, photochemistry, biocatalysis and so on.Polyacids and polyacids can be connected by M-O-M 'bond MN: transition metal.Organometallic skeleton (MOF) is also known as porous coordination polymer (PCPs), which has been developed rapidly because of its potential design topology and good application properties.As a new porous material, its synthesis can connect metal nodes (ions or clusters) and organic bridging ligands by coordination bonds.Due to the tunability of structure and function, it has been developed rapidly in synthetic chemistry and material science.Polyacids can be used as important inorganic building units to link with organic ligands or metal-organic ligands to synthesize new organic-inorganic hybrid compounds.This polyacid coordination polymer is sometimes called POMOFs.The study of polyacid coordination polymers has become a hot topic in the development of polyacid chemistry.In this paper, Zn- 蔚 -Keggin is used as the building unit, and the bidentate semi-rigid ligand 4- (4-carboxyphenoxyoxy-4) -4 carboxylieate (CPBPC) and the tridentate semi-rigid ligand 4O4 "-triazine-246-triyltriazine-246-triyltriazine-246-triazine-246-triazine-246-triazine-2-triazine-246-triazine-triazine-246-triazine-triazine-triazine-246-triazine-triazine-triazine-246-triazine-trioxylbenzoic acidTATAB) are used as the bridged ligand to form two inorganic organic heteropolymers based on polyacid under hydrothermal conditions.By adjusting the reaction conditions, such as pH value of solution, reaction temperature and ratio of raw materials, the optimum reaction conditions for the preparation of the target compounds were found and their properties were characterized.The compounds synthesized in this paper are: [TBA] 3 [PMov8Mo 鈪，

本文編號(hào)：1747753