A Cu I ‐Based Metallo‐Supramolecular Gel‐Like Material Built from a Library of ­Oligomeric Ligands Featuring Exotopic 1,10‐Phenanthroline Units

A 22‐membered cyclic alkene C 1 incorporating an exotopic 1,10‐phenanthroline nucleus in the ring skeleton has been synthesized and subjected to ring‐opening metathesis polymerization (ROMP) in dilute dichloromethane solution at varying monomer concentrations ( c mon ). The resultant libraries of macrocyclic oligomers were used as ligands for the generation of main‐chain metal–ligand oligomeric/polymeric complexes taking advantage of the strong affinity of 1,10‐phenanthroline derivatives for Cu I . The formation of a gel‐like material only upon addition of [Cu(CH 3 CN) 4 ]PF 6 to the most concentrated library ( c mon = 60 m M ) was explained as arising from the presence of significant amounts of trimeric and higher oligomeric macrocycles C i ( i ≥ 3), acting as cross‐linking components.