Encapsulation of ruthenium(ii) with macrobicyclic dioxime-functionalized ligands: on the way to new types of DNA-cleaving agents and probes

The clathrochelate di- and tri-ribbed-functionalized ruthenium(II) tris-dioximates with alkylamine, thioaryl, thioalkyl, phenoxyl, and crown ether substituents in alpha-dioximate fragments have been synthesized starting from reactive hexachloride clathrochelate precursors, formed by cross-linking with phenyl-, n-butyl- and fluoro-boronic capping groups. The IR, UV-vis, H-1,C-13 NMR and luminescent spectra as well as X-ray data for complexes obtained have been discussed. The redox characteristics (from cyclic voltammograms) for ruthenium(II) clathrochelates have been correlated with the electrochemical parameters of the corresponding iron(II) complexes and sigma(para) constants for functionalizing substituents.