| In recent years, many chemists and material scientists have paid their attentions to the supramolecular complexes due to their potential applications in catalysis, nonlinear optics, electronics, magnetism, gas adsorption and ion exchange etc. Because the properties of complexes depend on their structures, it is important to rational design and synthesis supramolecular complexes with specific structure and topology. However, the structures of supramolecular complexes are influenced by many factors such as ligands, counterions, geometry requirements of metal ions, solvent, pH value in the reaction system and templates etc. Among all of these, the ligands play the essential role, so rational design of ligands is most important in the construction of novel supramolecular complexes.In the past decade, a number of metal complexes with oxazoline-containing ligands have been used in catalytic reactions due to the intrinsic advantages of oxazoline-containing ligands, such as easy accessibility, stability towards hydrolysis and oxidation, and facile coordination to a wide range of transition metal ions. However, the reports on the supramolecular complexes with oxazoline-containing ligand are rare. As the expansion and extension of our previous work, we designed and synthesized four new oxazoline-containing rigid ligands 1,4-di(2-oxazolinyl)benzene (L1),4,4’-di(2-oxazolinyl)biphenyl (L2), 1,3-di(2-oxazolinyl)benzene (L3),4-(2-oxazolinyl)pyridine (L4), and investigated the assembly reactions of the ligands with varied Ag(I) salts, as well as the influences of anions, auxiliary ligands on the structures of supramolecular complexes. The properties, such as catalysis, SHG effect, fluorescence and ferroelectric property, of the complexes were also studied. There are four main parts in this thesis.1. Syntheses, Crystal Structures and Catalic Properties of Ag(Ⅰ) Complex with L1A new Ag(Ⅰ) complex with formula [Ag(L1)(NO3)] (1), has been synthesized by reaction of 1,4-di(2-oxazolinyl)benzene (L1) with AgNO3. Each Ag(Ⅰ) atom is coordinated by two different L1 ligands, and a nitrate, while each ligand connects two different Ag(Ⅰ) to form 1D Zigzag chain. Interestingly, complex 1 catalyzes three-component reaction of aldehydes, amines and phenylacetylene to give propergylamines in one-pot under the mild conditions. As the reaction condition is simple and the yields are satisfactory, we believe that this method may be widely used in the preparation of propergylamines.2. Syntheses, Crystal Structures and Properties of Ag(Ⅰ) Complexes with L2 and AgOOCCF3Three new coordination complexes [Ag2(L2)2(CF3COO)2] (2), [Ag(L2)0.5(CF3COO)] (3), [Ag(L2)2](CF3COO)2(H2O)2 (4), were obtained by the reactions of AgOOCCF3 with 4, 4’-di(2-oxazolinyl)biphenyl (L2) under different conditions. Complex 2 is a 1D chain, which is connected by the hydrogen bonds to form 3D structure. Complex 3 is a 2D network, and the adjacent layers are connected by the hydrogen bonds to form 3D structure. When the imidazole was added in the reaction of L2 and AgOOCCF3, complex 4 was obtained. The silver(Ⅰ) is four-coordinated in complex 4. Each L2 connects two Ag(Ⅰ) and each Ag(Ⅰ) is coordinated with four L2 to form a 2D structure, which is further linked together by hydrogen bonds to form 3D structure with a 8.2×6.8 A2 channel occupied by anions. It is interested that complex 4 can selectively catalyze the reaction of methyl 2-(eneamino)acetate and methyl acrylate. The photoluminescence properties of complexes 2-4 were also studied.3. Syntheses, Crystal Structures and Properties of Ag(Ⅰ) Complexes with L3 LigandSeven new complexes [Ag2(L3)2](NO3)2 (5), [Ag2(L3)2](C104)2 (6), [Ag3(L3)4](SbF6)3 (7), [Ag2(L3)2(CH3CN)2](PF6)2(8), [Ag2(L3)2(CH3SO3)2](CH3OH)2(9), [Ag4(L3)4](BF4)4 (10)' [Ag2(L3)2(CF3SO3)2] (11) have been prepared by reactions of 1,3-di(2-oxazolinyl)benzene (L3) with varied Ag(I) salts. Complexes 5 and 6 have the same sixteen ring structure, in which the oxygen atoms of nitrate and perchlorate weakly interact with the Ag(I). The sixteen ring structure is connected by the Ag…O interactions and hydrogen bonds to form the 3D structure. Complex 7 crystallizes in a chiral space group (C2). In 7, there are two connected sixteen ring structures with two-and four-coordinated silver atoms. The sixteen ring structure is bridged by the hexafluoroantimomate to form the 3D structure. Complex 8 has two kinds of sixteen rings, which are different from 7, but similar to those in 5 and 6. The silver is three-coordinated in 8, by the L3 ligands and acetonitrile molecule, which is different from those in 5 and 6. Although complexes 9 and 11 crystallize in different space groups, they have the same structure. The anions coordinate with the silver, which is different from those in other complexes. In complex 10, the L3 adopts trans-conformation to link four different Ag(I) atoms to form an infinite ID helical chain, which is different from the other complexes, in which, the L3 adopts cis-conformation. The 1D helical chains are further bridged by the tetrafluoroborate anions to form 3D structure. The results revealed that the nature of the counteranions has great impact on the structure of the complexes. Furthermore, the SHG and ferroelectric property of complexes 7 and 10 have been studied.4. Syntheses, Crystal Structures and Properties of Ag(I) Complexes with L4Eight new complexes [Ag(L4)](BF4) (12), [Ag(L4)](ClO4) (13), [Ag(L4)](PF6) (14), [Ag(L4)](CF3SO3) (15), [Ag3(L4)2(NO3)3] (16), [Ag3(L4)4(CH3CN)2](SbF6)3(H2O) (17), [Ag(L4)(OOCCF3)] (18) and [Ag(L4)(CH3SO3)] (19) have been obtained by reactions of 4-(2-oxazolinyl)pyridine (L4) with varied Ag(I) salts. The X-ray crystal structure analysis revealed that 12、13、 14、15 have the same 1D Zigzag chain structure, which is further connected by hydrogen bonds to form the 3D architecture. There are three two-coordinated, two four-coordinated and two five-coordinated Ag(I) atoms to give 1D Zigzag chains and 2D networks in complex 16. The adjacent 1D chains are connected by hydrogen bonds to form 2D layers. Furthermore, the hydrogen bonds link the 2D networks to generate 3D structure with …ABAB… arrangement. In 17, the subunit with two L4 and one two-coordinated Ag(I) connects the 1D Zigzag chains composed of L4 and four-coordinated Ag(I) to form a 2D network. The adjacent 2D layers are bridged together by the SbF6- to form a 3D structure. In complex 18, the anion acts as the bridged ligand, linking the 1D Zigzag chains which is similar to that in 17 to give a 2D structure. The adjacent 2D networks are connected by the hydrogen bonds to form 3D structure. There are two different kinds of Ag(I) in 19 with three-and four-coordination, respectively.In 19, the anion has two coordination modes: monodentate and bidentate. There are two different structures in 19, one is 1D Zigzag chain which is similar to 12 but different from 16, and the other one is 2D network which is consist of the adjacent 1D Zigzag chains connected by the anions. In addition, complexes 12-19 are studied by the electrospray mass spectrometry.In this thesis,19 complexes have been synthesized by reactions of L1, L2, L3 or L4 with different silver salts and structurally characterized. The influences of counteranion and ligand on the structure of the complexes have been investigated. We also studied the catalytic, photoluminescence, SHG and ferroelectric properties of the complexes. |
PDF Full Text Request