Synthesis And Properties Of Cyclophane Bridged Metallic Ruthenium Complexes With π-π Effect

With the rapid development of electronic products and the gradual improvement of people living standard, people hope more powerful function as well as more decreasing size of electronic products. The nature of electronic products is electronic intercommunication. Metal-Organic frameworks which is used to explore the nature of electronic products is one of the most ideal model. It is a hybrid of organic bridge and active metal center. The conjugation extent and length of the bridge ligands have directly effect on the electron transport process. In order to fine-tune the electronic transfer, we replace the conjugation bridge with cyclophane unit of π-π effect. The purpose of electronic interaction by π-π effect will be achieved.Extensive literature research demonstrate that [2.2]cyclophane unit is of strong π-π effect, which can used as bridge to perform electron transfer performance. We found dithia[3.3]cyclophane also exist weak π-π effect, when we synthesis [2.2]cyclophane unit. Whether or not can dithia[3.3]cyclophane transfer electron, have received less attention. So we take dithia[3.3]cyclophane unit as bridge ligands, attached metal with end. We systematic studies dithia[3.3]cyclophane on effects of metallic ruthenium complexes as electron transfer. This article details are as follows:1. Two metallic ruthenium vinyl complexes and two ruthenium acetylide complexes have been designed and synthesized, in which "[(PMe3)3(CO)Cl]RuC=C-" and "(η2-dppe)(η5-C5Me5)RuC=C-" are connected by dithia[3.3]metacyclophane unit. These complexes have been characterized by elemental analyses, NMR, MS, IR and X-ray crystal diffraction. The crystal structure of complex2-12exhibits relatively parallel position of the up and down benzene ring, of which the vertical and offset distance is2.98A and2.10A respectively. Electrochemistry studies illustrate that double metal compond can not show two separated one-electron oxidation waves. The peak separation of the two oxidation waves for it suggest a weak electronic interaction. The bridge ligands of dithia[3.3]metacyclophane cannot efficiently transfer electron. 2. Four ruthenium vinyl complexes and four ruthenium acetylide complexes have been designed and synthesized, in which "[(PMe3)3(CO)Cl]RuC=C-" and "(η2-dppe)(η5-C5Me5)RuC=C-" are connected by dithia[3.3]metaparacyclophane unit. These complexes have been characterized by elemental analyses, NMR, MS, and IR. Electrochemistry studies illustrate that double and three metal compond exhibit two separated one-electron oxidation waves. The peak separation of the two oxidation waves for them suggest a strong electronic interaction by C-H…π effect. Dithia[3.3]metaparacyclophane can efficiently transfer electron.