Multifunctional ferrocene-ruthenocene dyads linked by single or double aza-containing bridges displaying metal-metal interactions and cation recognition properties

The synthesis, electrochemical, electronic, and cation sensing properties of the ruthenocene-terminated 2-aza-1,3-butadiene 2, linear ferrocene-ruthenocene dyads 3 and 5, and the new structural motifs diaza[4.4]ruthenocenophane 7 and mixed ferrocene and ruthenocene metallocenophanes 8 and 10 are presented. The properties of these compounds have been systematically varied by introducing the ferrocene and ruthenocene moieties at the 1- or 4-position of the unsymmetrical 2-aza-1,3-butadiene bridge. Spectroelectrochemical studies of compounds 3 and 8, in which the ruthenocene unit appended at the 1-position of the bridge exhibits a rather unusual electrochemical behavior, revealed the presence of low-energy bands in the near-infrared (NIR) region in the partially oxidized forms, at 1070 and 1163 nm, respectively, which indicate the existence of intramolecular charge transfer between the iron and the ruthenium centers. The electrochemical and intermetallic charge-transfer (MMCT) studies (H-AB, lambda and alpha parameters) indicate that the 3(center dot+) and 8(center dot+) systems belong to the Class II classification for a mixed-valence compound. In addition, the low-energy (LE) band of the absorption spectra of all compounds prepared, except compound 10, are red-shifted by complexation with divalent Mg2+, Zn2+, Cd2+, Hg2+, and Ni2+ metal ions. For open dyads, biruthenocene compound 2 exhibited the higher red-shift by 92 nm, whereas for closed compounds the [4.4]ruthenocenoferrocenophane 8 displayed a remarkable red-shift by about 180 nm for Zn2+, Cd2+, Hg2+, and Ni2+ metal ions and by about 146 nm for Mg2+ cation. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. The experimental data and conclusions are supported by DFT computations.