Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1323122 | Journal of Organometallic Chemistry | 2012 | 9 Pages |
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•+, 22+ 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.
Graphical abstractThe 4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane radical cation features two mutually insulated ferrocenyl subunits despite a sizable redox splitting of 112 mV for their consecutive oxidation.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► 4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane has been synthesized via Heck reaction. ► Electrochemistry shows a splitting of redox waves for 4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane, 2. ► Spectroelectrochemical measurements reveal the absence of electronic coupling in 2+. ► DFT calculations reveal that the NIR absorption of 2+ is due to Fe (d-d) transitions.