Charge transfer through isomeric unsaturated hydrocarbons. Redox switchable optical properties and-electronic structure of substituted Indenes with a pendant ferrocenyl

A family of (ferrocenyl)indenes, (2-ferrocenyl)indene, (2-ferrocenyl)tetramethylindene, (2-ferrocenyl)hexamethylindene, (3-ferrocenyl)indene, and (3-ferrocenyl)hexamethylindene, and the corresponding monooxidized cations have been prepared. The results of a structural and spectroelectrochemical study are discussed. The availability of pairs of isomers with known geometries and differently methylated indenes allowed the detailed investigation of how slight geometric and electronic modifications affect their physical properties. The molecular structures have been determined by X-ray diffraction and compared with the fully optimized structures calculated with state-of-the-art DFT methods. Calculated and crystallographic structures agree in establishing the dependence of the orientation of the indene moiety and the ferrocenyl cyclopentadienyl rings on the degree of methylation. The UV-vis spectra and in particular the appearance upon oxidation of a new near-IR absorption, whose energy and intensity increase with the degree of methylation and cyclopentadienyl-indene planarity, are rationalized in the framework of the Hush theory and at quantum chemistry level by DFT and TD-DFT calculations.