Study On Synthesis And The Characteristic Of Vinyl-bipyridine Derivatives And Cu(I) Complexes

With the exciting developments of technongy and popularization of computer, the transmission and memory of information data is highly requested. So it becomes the hot research that how to develop the photoswitch materials which have the ability of high density information storage, high response speed and circulation.It is well known that the researches of stilbene derivatives have application prospect as the molecular photo-memory and photoswitch materials. What is more, polypyridine groups, owning high quantum production rate and good thermostability, have good coordinate ability, and Cu(I) complexes with the low price have well photophysical characteristic, which have attracted much attention due to their application to molecular components, photo sensors, nonlinear optics and so on. In this paper, three new bipyridine Ligands containing vinyl and Ferrocenyl were synthesized. They were 2-(4-(6-(pyridin-2-yl)pyridine-2-yl)-styryl)pyridine (L1), 6-(4-Ferrocenylvinylphenyl)-2,2'-bipyridine(L2),4-(4-Ferrocenylvinylphenyl)-6-phe-nyl -2,2'-bipyridine(L3) and their mononuclear Cu(I) complexes [Cu(L1)₂](BF₄) and heteronuclear Fe(II)-Cu(I) complexes [Cu(L2)₂](BF₄),Cu₂(L2)₂(μ-I)₂,[Cu(L3)₂](BF₄) and Cu₂(L3)₂(μ-I)₂. Their characterized structures and their photo electric character were also studied. And we received some meaningful results.1. The crystal structure of mononuclear complex [Cu(L1)₂](BF₄) was a distorted tetrahedron constructed with the center Cu(I) and four N atoms, and the vinyl parts are trans styles. Absorption and electrochemical properties showed that ligand L1 and its complex [Cu(L1)₂](BF₄) have very good photo isomerization in the light of 365 nm. The photoisomerization reactions have influenced their reversible redox propreties. They maked E_1/2 in a negative shift (0.2030 V, 0.1885V and 0.1715 V) andΔE was gradually increasing trend (0.096 V, 0.099V and 0.131 V).2. From the ligand L2 and its heteronuclear Fe(II)-Cu(I) complexes [Cu(L2)₂](BF₄) and Cu₂(L₂)₂(μ-I)₂. The absorption spectraes showed that one absorption peak of ligand L2 in 462 nm was attributable to the LMCT of Ferrocenyl, and heteronuclear Cu (I) complex in the 485 nm and 450 nm absorptions was attributable to the MLCT absorptions from Cu (I) to ligand. Meanwhile, absorption and electrochemical properties showed that ligand L2 and its Cu (I) complexes had very good photoisomerizations in the light of 365 nm. The photoisomerization reactions had influenced their reversible redox propreties. They maked E_1/2 of L2 in a negative shift (0.0895V, 0.088V, 0.0855V) andΔE was gradually increasing trend (0.057V, 0.066V, 0.071V). While theΔE and E_1/2 changes of Cu⁺/Cu²⁺ in [Cu(L2)₂](BF₄) were on the contrary, and the changes in Cu2(L2)₂(μ-I)₂ were irreversible.3. The crystal structure of ligand L3 showed that double bond C23=C24 was anti-structure, and pyridine, benzene ring and ferrocene were almost total plane. Absorption and electrochemical properties showed that the isomerization reactions of ligand L3 and its Cu (I) complexes in the 365 nm light affected unobviously their the oxidation - reduction reaction.