Synthesis and Binding Properties of Dendritic Oxybathophenanthroline Ligands towards Copper(II)

Dendritic oxybathophenanthroline ligands (generation 0 to 3) have been synthesized by treatment of 4,7-bis(4´-hydroxyphenyl)-1,10-phenanthroline with the corresponding Fréchet-type dendrons carrying a benzylic bromide function at the focal point. The complexation of copper(II) has been studied by liquid-liquid extraction using the radioisotope ⁶⁴Cu and time-resolved laser-induced fluorescence (TRLFS) measurements in organic media proving the formation of 1:3 complexes (Cu : dendritic ligand). The stability of the copper complexes is mainly determined by the 1,10-phenanthroline core element. The stability constants of the 1:3 complexes were found to be in the order of log K ~ 16 in CHCl₃. On the other hand, increasing generation of the dendritic Fréchet-type branches leads to enhanced shielding of the copper ion from the environment. Additional information about this behaviour was obtained by the fluorescence lifetimes which are much less influenced upon addition of copper(II) salt to solutions of the higher generation ligands.