Nine chromophores with ferrocene donor and pyridine/pyridinium acceptors have been prepared and further investigated. The performed X-ray analysis showed partially polarized and geometrically oblate pyridine unit. An extension of the π-system and N-quaternization were revealed as suitable tools for exclusive manipulation of the LUMO with the almost steady HOMO. Whereas the electrochemical HOMO-LUMO gap can be tuned from 3.01 to 1.49 eV, the high- and low-energy absorption bands were found within the range of 280-402/456-547 nm. The pyridinium chromophores showed distinct negative solvatochromism. A thorough DFT analysis has been performed; it turned out that ferrocene donor is capable of two principal D-A interactions, whose employment depends on the appended electron-withdrawing moiety.
This journal is © The Royal Society of Chemistry.