A CuI-Based Metallo-Supramolecular Gel-Like material built from a Library of oligomeric ligands featuring exotopic 1,10-Phenanthroline units

A 22-membered cyclic alkene C1 incorporating an exotopic 1,10-phenanthroline nucleus in the ring skeleton was synthesized and subjected to ROMP in dilute dichloromethane solution at varying monomer concentration (cmon). The resultant libraries of macrocyclic oligomers were used as ligands for the generation of main-chain metal-ligand oligomeric / polymeric complexes making use of strong affinity of 1,10-phenanthroline derivatives for CuI. The formation of a gellike material that occurred only upon addition of Cu(CH3CN)4PF6 to the most concentrated library (cmon = 60 mM) was explained as arising from the presence of significant amounts of trimeric and higher oligomeric macrocycles Ci, with i ≥ 3, acting as cross-linking components.