| Copper(I) coordination complexes have been extensively investigated because of their interesting structures and chemical, physical properties. The nature of ligand, the flexibility and rigidity of organic linkers, the Cu I-to-ligand ratios, the reaction temperature, the reaction solvents play an important role in directing the structural formats of copper(I) complexes. In this thesis, we synthesized a family of((pyridinyl)-1H-pyrazolyl) pyridine(pypzpy) ligands with the same N-heterocyclic groups but different coordination sites. Then, we carried out the reactions of these pypzpy ligands along with their methyl derivatives with Cu I and isolated copper(I) complexes of different structures. The coordination site of the ligands also imposed effects on their structures and properties1.The nine pypzpy ligands(2,2’-, 3,2’-, 4,2’-, 2,3’-, 3,3’-, 4,3’-, 2,4’-, 3,4’-, 4,4’-pypzpy) were synthesized by the reactions of(1H-pyrazolyl)pyridine and iodopyridine. Reactions of pypzpy ligands with Cu I at different temperatures yielded 11 Cu(I)/pypzpy complexes [{(2,2’-pypzpy)Cu}(?-I)]2(1), [{Cu3(μ3-I)3}(μ-3,2’-pypzpy)]n(2), [{Cu2(μ-I)(μ3-I)}2(3,2’-pypzpy)2]n(3), [{Cu(μ3-I)}2(4,2’-pypzpy)2{Cu(μ-I)}2]n(4), [{Cu3(μ3-I)3}(μ-2,3’-pypzpy)]n(5), [(Cu I)(μ-2,3’-pypzpy)]2(6), [(Cu2I2)(3,3’-pypzpy)](7), [(Cu I)(4,3’-pypzpy)](8), [{Cu(μ3-I)}2(μ-2,4’-pypzpy)2{Cu(μ-I)}2]n(9), [(Cu I)(3,4’-pypzpy)](10) and [(Cu I)(μ-4,4’-pypzpy)]n(11). Complex 1 contains a normal [Cu(μ-I)]2 dimeric structure. Complexes 2 and 5 consist of a unique displaced staircase chain [Cu2(μ3-I)2]n. Complex 3 has a 2D network formed by linking chairlike [Cu2(μ-I)(μ3-I)]2 units with two pairs of 3,2’-pypzpy bridges. Complexes 4 and 9 have a rare 1D triple chain, in which one internal 1D ladder-like chain [Cu2(μ3-I)2]n is connected with two zigzag chains [Cu(μ-I)]n via 4,2’-pypzpy or 2,4’-pypzpy ligands. Conplex 6 consists of two [Cu I] units interconnected by two 2,3’-pypzpy ligands. Conplex 11 contains a 1D chain assembled by monomeric [Cu I] units and 4,4’-pypzpy ligands. The influence of the coordination sites of pypzpy ligands on the coordination modes, the [Cun In] units and the [Cun In]-based complexes along with their luminescent properties were studied.2. Reaction of pypzpy and CH3 I produced a series of single methylation ionic ligands 1-methyl-3-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide([3,2’-pypzpym]I, 1-methyl-4-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide([4,2’-pypzpym]I), 1-methyl-4-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide([2,4’-pypzpym]I), 1-methyl-3-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide([2,3’-pypzpym]I) and a series of double methylation ionic ligands 1-methyl-3-(1-(1-methylpyridin-1-ium-4-yl)-1H-pyrazol-3-yl)pyridin-1-ium diiodide([3,4’-pypzpydm]I2), 4,4’-(1H-pyrazole-1,3-diyl)bis(1-methylpyridin-1-ium) diiodide([4,4’-pypzpydm]I2), 3,3’-(1H-pyrazole-1,3-diyl)bis(1-methylpyridin-1-ium) diiodide([3,3’-pypzpydm]I2), 1-methyl-3-(3-(1-methylpyridin-1-ium-4-yl)-1H-pyrazol-1-yl)pyridin-1-ium diiodide([4,3’-pypzpydm]I2). Reactions of these ligands with Cu I resulted in the formation of [(Cu I2)(3,2’-pypzpym)](12), [(Cu4I6)(3,2’-pypzpym)2]n(13), [(Cu4I6)(4,2’-pypzpym)2](14), [(Cu I2)(2,3’-pypzpym)](15), [(Cu I3)(3,3’-pypzpydm)](16), [(Cu I3)(4,3’-pypzpydm)}](17), [(Cu I2)(2,4’-pypzpym)](18), [(Cu3I7)(3,4’-pypzpydm)2](19) and [(Cu I7)(4,4’-pypzpydm)3](20), repectively. Conplexs 12-20 were characterized by IR, elemental analysis, and 12-15 were also characterized by single crystal X-ray crystallography. Under O2, some complexes displayed high catalytic activity toward the N-arylation of nitrogen-containing heterocycles. |
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