Study Of Structural Chemistry Of Cu～Ⅰ-Cu～Ⅱ Mixed Valence Halo-cluster Complexes

System containing a metal in two valence states has been connected with theelectron transport in organism and material properties of optics, electricity ,magnetism, and become an appealing area and hot research field because of their greatpotential applications in many fields, such as piament, ceramic, mineral, chemistry,biocatalysis system , superconductive materials and so on .Electron transfer betweenCu (â… ) and Cu(â…¡) is of central important in a vast range of chemical andbiochemical catalytic systems. Copper(â… )- Copper(â…¡) electron transfer is alsointrinsically interesting in comparison with studied iron, cobalt, and rutheniumelectron-transfer couples, and this study may reveal about structural changesaccompanying oxidation and reduction of copper in metalloenzymes. At the same time,consideraable attention has been paid to the basic problems of the mixed valencechemical fields involving in color theory, catalytic action, photochemistry andmetal-metal bonding. Therefore, work on this area is very important and significant interests. Thedissertation focus on the synthesis , stuctrue and characterization of Cuâ… -Cuâ…¡ mixedvalence complexes and intends to reveal their rich structure chemical features. So farwe had made achievements on such aspects: 1. Synthesized twelve novel mixed valence complexes,determined the structures of these compounds by X-ray single crystal diffraction technology. They were [CuCl(phen)2][CuCl2] (â… )ï¼›[Cu3Br3(phen)5]2[CuBr2]2[Cu2Br4](H2O)2 (â…¡)ï¼› [Cu(phen)2Br][Cu2Br3] (â…¢)ï¼›[Cu(phen)2Br]2 [Cu4Br6]．C2H5OH(â…£)ï¼› [Cu4(Ophen)4(Cu2Br4 )] (â…¤)ï¼›[Cu3 I2 ( phen)6]I3.H2O (â…¥)ï¼› [CuI(phen)2][Cu3I4](â…¦)ï¼› [Cu2(OH)2(phen)2][Cu4I6] (â…§)ï¼› [CuBr2(phen)]2 (â…¨)ï¼› [Cu3 I3( phen)2] (â…©)ï¼›[CuI(phen)] (â…ª)ï¼› (Hphen)(CuI2)．　１．５H2O (â…«).　Ａｍｏｎｇ　ｔｈｅｓｅ　ｃｏｍｐｏｕｎｄｓ,　(â… )^â…§ have been the mixed valence system, the others only have Cuâ… or CuⅡ． Being the iii福州大学硕士学位论文 assistant ligand, different halogen can not only balance the structural charge but also help to design various copper-halo cluster as a result of wide variety of copper's coordination geometry and the bridging capability of the halide ions.2. The effects of reaction conditions on the outcome phase are considered and studied systematically.We have conquered the difficulties that unstability of product at high temperature and contens cannot diffuse efficiently at low temperature, and find a convenience path for synthesizing mixed valence system.3. The complexes have been characterized by IR and solid fluorescence spectra.The relationship between the structure and the properties are investigated and some interesting experimental results are obtained. The solid fluorescence spectra show Cuâ… -Cuâ…¡ mixed valence complexes possess broad absorbed peaks at 300⁴00ｎｍ and weak absorbed peaks at VIS wave range , but the compounds with Cu+ atom only show the 200⁴00ｎｍ absorption .4. DFT/BLYP calculation was carried out to study the nature of bonds and the electronic structure of two compounds containing delocalized mixed-valence Cu2 centers and compound (â…¤) with its isomer and find the relationship between molecular aymmery and energy.