| Porous coordination polymers (PCPs) with designable and dynamic cavities have great potential applications as novel and functional materials. In recent decades, the post-synthesis of PCPs is becoming more and more popular in order to further investigate their unique functions as efficient materials in the areas of storage, separation, catalysis, magnetism, and conductivity etc. This work focused on the syntheses and self-assemble habits of PCPs based on a series of mixed small molecules which were used as ligands with N, O coordinated atoms, such as azole and their derivatives, aromatic acid and amino substituted carboxylic acids, and the relationship between their properties and structures were demonstrated and analyzed. Furthermore, after comparing those eighteen complexes exhibiting one-dimensional, two-dimensional as well as three-dimensional structures, we found that the coordination modes of those small ligands have great effect on the structures of these compounds which provided some rules of self-assemble for PCPs in the long run. The thesis is divided into four chapters.In the first chapter, the study background of this work is introduced which include the current survey of PCPs with the emphasis on the summarized achievements, some basic principles on self-assemble of PCPs and their functional post-synthetic modifications. Finally, the significance of this work based on PCPs was completely explained.In the second chapter, triazole or tetrazole and multi-bridged inorganic anions were used as mixed ligands to generate five complexes [Zn2(ata)(OH)(SO4)(H2O)]n·2nH2O (1) ,[Cd(atrz)(Cl)(SO4)0.5]n·2nH2O (2),[Zn2(trz)(MoO4)(OH)]n (3), [Zn3(datrz)2(MoO4)2]n (4) and [Zn(Him)(MoO4)(H2O)]n (5). ( Hata = 5-amino-1H-tetrazole , Hatrz = 3- amino-1H-1,2,4-triazole,Hdatrz = 3,5-diamino-1H-1,2,4-triazole,Htrz = 1H-1,2,4-triazole ,Him = 1H-imazole).How the coordination modes of those ligands in Zn(II), Cd(II) complexes affected the whole multi-dimensional structures of self-assembled polymers was investigated. Also, those polymers exhibited higher thermal stability and strong luminescent emissions at room temperature which demonstrate that those polymers can be used as potential inorganic-organic hybrid fluorescent materials.In the third chapter, a series of PCPs have been successfully synthesized under hydrothermal conditions, mainly based on Zn(II)/trz system mixed with higher symmetric aromatic carboxylic acids, such as terephthalic acid, trimetric acid, 1,2,4,5-benzenetetracarboxylic acid, etc. Single-crystal structural analysis of those PCPs, [Zn2(bdc)(Hbdc)(trz)(H2O)]n·2nH2O (6), [Zn(bdc)(Hpz)(H2O)]n (7), [Zn4(atrz)2(btc)2(H2O)3]n (8), [Zn2(datrz)(btc)]n·nH2O (9), [Zn2(datrz)(Hbtec)]n·1.5nH2O (10) , [Zn3(datrz)2(btec)]n·1.5nH2O (11), [Zn3(atrz)2(btec)(H2O)2]n·1.5nH2O (12), [Zn2(atrz)2(bdc)]n·nH2O (13) (H2bdc = terephthalic acid, Hpz = 1H-pyrazole,H3btc = trimetric acid,H4btec = 1,2,4,5-benzenetetracarboxylic acid), demonstrated that azole ligands inclined to form symmetric Zn4(trz)2 cluster units, which could be linked each other to form zigzag chains or two dimensional layers. At the same time, carboxylic acid behaving as bridged ligands could be used as linkers or to build two-dimensional layers. Thus, the whole three-dimensional architectures could be viewed as constructed by low-dimensional building units. Moreover, the size of cavity of porous PCPs is mainly controlled by the length of linkers as well as the"symmetry index"of the two-dimensional layers. Finally, those PCPs obtained in this chapter exhibited very strong blue or yellow photoluminescence. In the fourth chapter, amino substituted carboxylic acid such as aminotriacetic acid (H3NTA) and ethylenediaminetetraacetic acid (H4Y) were added into Zn(II)/trz system under hydrothermal conditions. Four complexes [Zn2(datrz)(NTA)]n·0.5nC6H6 (15), [Zn2(atrz)(NTA)]n·0.5nC6H6 (16) , [Zn3(datrz)2(Y)]n·3nH2O (17) and [Zn5(atrz)(Y)2]n·6nH2O (18) (H3NTA = aminotriacetic acid, H4Y = ethylenediaminetetraacetic acid), were synthesized. We found that the reactant solvents can be selected in the cavities of these porous PCPs. In addition, some bimetallic complexes were obtained if another metal ion was added into the above reaction system.In the fifth chapter, a briefly conclusion on this work and an outlook have been viewed.
|
PDF Full Text Request