Synthesis of macrocyclic phenanthrolines with exotopic binding sites. Probing their complexation behavior with copper(I) and iron(II)

Starting from 4,7-dichlorophenanthroline ( 1 ) a synthetic approach is developed to novel macrocyclic mono- and bisphenanthrolines ( 5a – d , 6a – d ) with exotopic binding sites. As these coordinating compounds are characterized by a flexible spacer unit, their utility as ligand for the construction of oligomeric, dendritic and box-like structures in the presence of copper(I) and iron(II) is evaluated. Spectroscopic data suggest that with copper(I) the 1+1] adduct Cu₂( 6c )( 7 )]²⁺ is formed.