Studies On Synthesis And Properties Of Metallic Compounds And Macrocycles With Photochromic Units

In recent years, there has been confronted with higher challenge along with the frequent development of the science of information and related technology in the field of the micro-processor. In order to overcome the physical and technologic limits, some functional micro-devices such as molecular wires, molecular switches, molecular rectifiers and molecular storages have been designed and manufactured in molecule levels. So studies on molecular devices have received much attentation from the scientists who work on chemistry and science of material at present.Basic components of molecular devices are information storage materials with photochromic properties. To explore of novel structures and unique properties, some organometallic compounds and macrocycles withσ,σ-bridging azobenzene chains and dithienylethene units were designed and synthesized, and their characterization, photochromic properties will be described as following:1. The photochromism and related concepts were described, and the recent progress in the fields of the azo and dithienylethene systems was summarized. Furthermore, the C-M bond was introduced into these two systems and the unique shaped-modulated macrocycles were synthesized.2. The 4,4'-diethynylazobenzene was used as the starting material, which was treated with metallic ruthenium reagent and other ligands to give six bimetallic ruthenium compounds withσ,σ-bridging azobenzene chains. Their structures were confirmed by NMR, X-ray crystal diffraction and elemental analysis, and their electrochemical properties, photoisomerization properties and behavior of switch were described. The results indicated good photoisomerization properties and effects between metal atom and metal atom each other.3. The diformyl-substituded dithienylethene was used as the starting material, and six dithienylethene derivatives with ferrocene units were synthesized through Wittig reactions and Aldol reactions, respectively. Furthermore, the diethynyl-substituded dithienylethene was used as the starting material, which was treated with metallic ruthenium and gold reagents to give three metallic compounds. The structures of the complexes were confirmed by NMR, X-ray crystal diffraction and elemental analysis, and their photochromic properties and thermal stability were described. The results indicated that the ferrocenyl group could increase the thermal stability and electrochemical properties shown MLCT (metal-to-ligand change transfer).4. The dichloro-substituded dithienylethene was used as the starting material, and phosphor atom was introduced into dithienylethene units. Nine dithienylethene derivatives and three metallic compounds were synthesized, whose structures were confirmed by NMR, X-ray crystal diffraction and elemental analysis. Their photochromic properties, response times and quantum yields were described. The results indicated that the introduction of phosphor atom could advance the response time and increase quantum yields.5. The diformyl-substituded dithienylethene was used as the starting material, and six Schiffbase compounds with dithienylethene units were synthesized, whose structures were confirmed by NMR, X-ray crystal diffraction and elemental analysis, and their photochromic properties were described. In particular, emphasis was put on the effect of the metallic ion in photochromic properties. The results indicated that the open or closed state could be loched by metallic mercury ion, but the compounds would have photochromic properties underwent EDTA.6. The dichlor-substituded dithienylethene was used as the starting material, and three macrocycles with several thienylethene units were synthesized. Their structures were confirmed by NMR, X-ray crystal diffraction and MS, and their photochromic properties were described. The biggest macrocycle showed unique quantum yield, excellect thermal stability and outstanding fatigue resistance.