Synthesis, Photochemical And Photophysical Properties Study On Photo-functional Cu(Ⅰ) Compounds

With the information society coming, as the basis of information technology , photons attracted more attention than electrons little by little. Since the early reports on the observation of phosphorescence of a variety of phosphine, pyridine complexes of d10 metal centers appeared in the seventies of last century, work in this area of luminescent dlocomlexes , had been developing rapidly and gaining a lot of attention over the past years .Cu( I )complexes, as a kind of photo-functional materials, had played an important role. These complexes, because of variety of structures, novel photochemical and photophisical properties, had attracted more attention in many fields, such as OLED, sensor materials, NLO and so on. In this paper, a series of model compounds were synthesized. Their molecular structures were determined by X -ray diffraction. The research on their photochemical and photophisical properties , especially the attribution of excited states, had been carried out by spectra of UV-Vis, spectra of emission and spectra of excitation. Moreover, the sensitive properties in different environment and LB films of [Cu2(tdpme)2 (4-4 bpy) ][BF4]2 were also discussed in this paper.I.We designed and synthesized several new complexes such as [Cu(tdpme)]I, [Cu(tdpme)]PF6, [Cu2(Phen)2]I2 and [Cu2(tdpme)2 (4-4 'bpy) ][BF4]2. Their structures had been determined by X-ray diffraction. In addition, looking tdpme as a model ligand, we designed a new ligand btdpmb which was a tridentate or hexadentate soft ligand with a B3N3 ring in the structure. After btdpmb had been determined primarily, we let it react with Cul and [Cu(CH3CN)4]BF4 respectively. The following result was that, when B2 reacted with Cul, not only N, but also P had coordinated with Cu in the reaction(This can be inferred from the UV-Vis spectrum) . While only P coordinated when it reacted with [Cu(CH3CN)4]BF4.2. The absorption ,emission and excitation spectra of the materials also had been studied.Compound [Cu(tdpme)]I displayed blue luminescence with an emission maximum at 490nm in solid state, an absorption maximum at 299.14nm in CH2C12 and 279.78nm in CH3CN respectively. We suggested tentatively that the absorption can be attribute to the mixture of metal centred MC and ligand to metal LMCT charge transition. For compoud [Cu2(Phen)2]l2, a material with red emission , similar research had been carried out .We discovered that, there were three peaks in the absorption spectrum, 270nm, 290nm and a wide absorption from 300-380nm. The absorption had been suggested to result from n -* n 'transition, I to metal charge transition(XMCT) and metal to ligand (phen) charge transition (MLCT) respectively. Compound [Cu2(tdpme)2 (4-4 bpy) ][BF4J2 was a material with strong yellow emission when excited at 375nm at room temperature. Its emission maximum was 555nm in solid state. For this compound, the absorption spectra obtained showed obvious difference in different solvents such as CHaCh, CHsCOCHs, CH3OH or CH3CN. And this novel property was attributed to its sensitive nature .Therefore, we studied its sensitive properties in the following work.3. Compound [Cu2(tdpme)2 (4-4 bpy) JfBF.^ attracted more attention for its interesting sensitive properties. In order to conclude the MLCT excited states factor many experiments had been performed. In the process, we found it to shift quickly from yellow to orange red when met with very little C2H5OH ,CH3COCH3, CH3OH or CH3CN. For C2H5OH and CH3OH, the emission can recover little by little when the solvent vapoured slowly at room temperature. But this can not been observed for CH3COCH3 and CH3CN. Especially with CH3COCH3 , the emission maximum can shift from 555nm to 570.6nm. However, only after heating the emission can recover. And the following yellow emission maximum was not 555nm, but 545nm. Then we gave CH3COCH3 for the second time, the emission shifted to 570.6 nm again. The interesting phenomenon made us heat the solid for the second time. And the emission maximum again returned to 545nm. So, we concluded that once c...