| In this thesis, we have synthesized four new organic ligands (three monopyrazole ligands and one bipyrazole ligand), and eight complexes of the coinage metal gold(I) silver(I) and copper(Ⅰ, Ⅱ). These ligands and complexes were characterized by CHN microanalyses, IR spectra, H NMR etal. The structures of these complexes were determined by X-ray diffraction.Four organic ligands as follows: 3,5-diphenyl-1H-pyrazol-4-y1 benzoate (HL1) (E)-N-benzylidene-3,5-diphenyl-1H-pyrazol-4-amine (HL2) 3,5-diphenyl-lH-pyrazol-4-yl acetate (HL3) (E)-N-((E)-3-((E)-(3,5-dipheny1-1H-pyrazol-4-ylimino)methyl)benzylidene)-3,5-diphenyl-1H-pyrazol-4-amine (H2L4) The eight complexes and their molecular as follows: [CuI(PhCOOPh2Pz)]3 (1) [AgI(PhCOOPh2Pz)]3 (2) [AuI(PhCOOPh2Pz)]3 (3) [CuII(PhCOOPh2Pz)]6 (4) [CuII(PhCNPh2Pz)]6 (5) [AgI(PhCNPh2Pz)]3 (6) [CuI(AcOPh2Pz)]3 (7) [AuI(AcOPh2Pz)]3 (8)According to the different types of ligands and complexes, these 8 complexes can be divided into two categories.1. Trinuclear complexes:Complexes 1-3,6-8 were self-assembled with monopyrazole ligandsandcopper(Ⅰ), silver(Ⅰ), gold(Ⅰ). In these complexes, the monopyrazoles were deprotonated in the presence of base and bridged two adjacent metal centers to form the planar trinuclear structures.2. Hexanuclear crown complexes:Complexes 4,5 adopt discrete hexanuclear crown structures, built with copper(Ⅱ) and monopyrazoles. Theywere obtained by oxidization of trinuclear complexes mentioned abovein the presence of MeOH.The following conclusions can be drawn from the main results of this study.1. The monovalent coinage metals and monopyrazole ligands tend to form trinuclear nine-membered ring M3N6. The substituent of the pyrazole ring can influence the 7r-acidity/basicity of the trimers.2. For the studyof host-guest chemistry, DFT calculation and analysis indicate that 7r-acidity/basicity of nine membered ring center areinfluencednot only by the substituent constants, but also atomic species directly attached. |
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