Synthesis, spectroelectrochemistry and electronic structure calculations of 4-(2-ferrocenylvinyl)-[2.2]-paracyclophane and 4,12-di-(2-ferrocenylvinyl)-[2. 2]-paracyclophane

摘要

4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane 2 has been prepared and investigated with respect to its electrochemical and UV/Vis/NIR spectroelectrochemical properties. Cyclic and square wave voltammetric measurements show two consecutive one-electron oxidations with a moderate redox splitting of 112(±3) mV for the individual Fc/Fc + couples. In spite of this redox splitting, radical cation 2 ?+ is a class I mixed-valent system with no detectable electronic coupling between the individual redox sites as is shown by the comparison of the Vis/NIR spectra of 2 ?+, 2 2+ and the radical cation of 4-(2-ferrocenylvinyl)-[2.2]-paracyclophane, 4 ?+. The NIR bands observed for the oxidized forms have been assigned as ferrocene-based d-d transitions by quantum chemical calculations.