| In the past decades, copper(I) complexes have been attracted much attention by scientists in the world and then the research on them has been one of major fields on coordination chemistry, because of their intriguing diversity of structures, novel photophysical and photochemical properties. Recently copper(I) complexes contained diimine-type ligands( 2,2'-bipyridine, 1,10-phenanthroline and their substituted derivatives designated as diimine-type ligands) with strong visible absorption and highly luminescence have been fouced on in this field, since they may be used in various photochemical applications such as solar energy conversion, electroluminescent devices and water photoxygenation systems. The copper(I) complexes of phenanthroline derivatives have been extensively investigated and reported by David R. McMillin, Timothy B. Karpishin and co-workers. However, there are only a few studies in the copper(I) complexes of bipyridine derivatives now, so in this paper a series of copper(I) complexes contained derivative bipyridine ligands were designed and synthesized. Their structures were determined by X-ray diffraction. Moreover, the research on their thermal stability, photoluminescent properties as well as photoinduced electron transfer process was carried out by spetra of TG, spectra of UV-Vis, spectra of fluorescence and spetra of EPR. The main works are as follows:1. We designed and synthesized two new derivative bipyridine ligands such as 6-(4'-Methoxyphenyl)-2,2'-bipyridine(MeO-CNN)(Ll) and 6-(4'-hydroxyphenyl)-2,2' -bipyridine(HO-CNN)(L2).Their structures have been proved by the measurement methods of IR, MS, 'HMNR. Through using strategies for designing and organizing molecular, we succeeded in synthesizing one mono-nuclear copper(I) complex [Cu(MeO-CNN)2]BF4(l) and five di-nuclear copper(I) complexes [Cu2(MeO-CNN)2 (PCy3)2(w-4,4'-bipy)](BF4)2(2), [Cu2(MeO-CNN)2(PCy3)2(w-bpete)](BF4)2(3), [Cu2 (MeO-CNN)2(PPh3)2(w-4,4'-bipy)](BF4)2(4) , [Cu2(MeO-CNN)2(PPh3)2(w-bpete)] (BF4)2(5), [Cu2(MeO-CNN)2(PPh3)2(w-4,4'-azopy)](BF4)2(6). In these copper(I) complexes, ligand MeO-CNN was use as the major ligand, derivative bipyridine2004ligands [4,4'-bipyridine (4,4'-bipy), l,2-bis(4-pridyl)ethene(bpete), 4,4'-azo-pyridine (4,4'-azopy)] as the brdging ligand, phosphinidene ligands [triphenylphosphine (Ppha), tricyclchexylphosphine(PCy3)j as the minor ligand.2. The structures of the serial copper(I) complexes contained derivative bipyridine ligands have been determined and studied by X-ray diffraction. In all of these complexes, the coordination geometry aroud copper(I) is best described as pseudo-tetrahedron. The complex(l) is a mono-nuclear copper(I) complex with non-equivalence of its ligands which is resulted from n-n stacking interaction between the phenyl ring of one of the ligands and the pyridyl ring of another ligand, while the complex(2), (3), (4), (5) and (6) are all di-nuclear copper(I) complexes with a center of symmetry. In particular, the complex(4) can form one-dimensional chain supermolecular structure by TT-TT stacking interaction.. The thermal stability, photo luminescent properties and photoinduced electron transfer process of the serial copper(I) complexes contained derivative bipyridine ligands were investigated by spetra of TG, spectra of UV-Vis, spectra of fluorescence, and spetra of EPR. Firstly, we studied the thermal stability of these complexes according to their curves of TG. The results show that they have good thermal stability, particularly the mono-nuclear copper(I) complex has better. Secondly, The UV-Vis absorption spectra of these complexes had been studied. All of the complexes could exhibit a strong visible metal-to-ligand charge-transfer (MLCT) absorption. Their fluorescent spectra show that all the di-nuclear copper(I) complexes could exhibit good emission in red region, but the mono-nuclear copper(I) complex could not. We then study the possible fluorescent quenching process of complex(l) according to its absorption spectra in different solvents. A... |
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