Bis[4′-(4-anilino)-2,2′∶6′,2″- terpyridine]transition-metal complexes: electrochemically active monomers with a range of magnetic and optical properties for assembly of metallo oligomers and macromolecules

Abstract

The new ligand 4′-(4-anilino)-2,2′∶6′,2″-terpyridine (L ¹ ) and a range of its transition-metal complexes have been prepared. The crystal and molecular structures of L ¹ and [CuL ¹ ₂ ][PF ₆ ] ₂ have been determined. Model reactions show that L ¹ and its transition-metal complexes can be functionalised with suitable organic reagents: reactions with aromatic dianhydrides give imide derivatives, reactions with acid chlorides afford amide derivatives and benzoquinone reacts with L ¹ to give a quinonylanilinoterpyridine ligand, complexes of which are described, but not with the complexes of L ¹ . The use of L ¹ and its complexes in building up multicomponent architectures has been tested. Metallo-dimers and co-ordination polymers linked by new binucleating bis(terpyridyl) ligands have been prepared by two routes: (a) first coupling two L ¹ with difunctional organic reagents and then treating the new binucleating ligands with a metal source, or (b) preforming monomeric complexes of L ¹ and treating these with the same difunctional organic reagents. Analytical, spectroscopic and electrochemical data are given for all complexes; the chromophoric, magnetic and electrochemical properties of the complexes vary with transition metal and terpyridyl ligand substituent.