Selin R. Synthesis, structure and properties of the tris-dioximate asymmetric and fluorescently tagged iron(II) clathrochelate complexes

The PhD thesis is devoted to the development of methods of the synthesis and directed functionalization of mono-ribbed substituted tris-α-dioximate iron (II) clathrochelate complexes with fluorescent groups and studying of their properties. This will expand the available methods for the synthesis of macrobicyclic iron(II) complexes and will open the possibility of studying the mechanism of their biological activity by the method of molecular imagining. The comparative analysis and testing of most of the described synthetic approaches for the direct synthesis and modification of asymmetric monoribbed-substituted tris-α-dioximate iron(II) clathrochelate complexes was performed. Modified the reaction of nucleophilic substitution of chlorine atoms of iron (II) dichloroclathrochelate by aliphatic S-nucleophiles for directed synthesis of mono-substituted complexes. The directed rib functionalization reaction of halogen-substituted iron (II) clathrochelate was performed with palladium/copper-promoted C–C bond formation reaction (Sonogashira reaction) and hybrid iron (II) crown-clathrochelate complexes were obtained. Asymmetric propargylamine-containing iron (II) clathrochelate complexes were synthesized, their structure, electrochemical properties and stability in media close to biological were studied. A method of modification of iron (II) clathrochelate complexes with terminal reactive ethynyl groups by azide-containing fluorescent markers by Cu-promoted "click" cycloaddition reaction has been developed. Symmetric and asymmetric fluorescently tagged iron (II) clathrochelate complexes were synthesized. The influence of the clathrochelate framework on the fluorescent properties of tags of different structure, which differ significantly in their spectral characteristics, has been studied. For the most promising complexes, their interaction with globular proteins and localization in A2780 series cancer cells were studied.