Metal‐Mediated Synthesis of Multidomain Ligands—A New Strategy for Metallosupramolecular Chemistry

The bridging ligand bis{4′‐(2,2′:6′,2″‐terpyridinyl)}ether ( 1 ) can be prepared in 69% yield from the reaction of 4′‐chloro‐2,2′:6′,2″‐terpyridine ( 3 ) with 2,2′:6′,2″‐terpyridin‐4′(1′ H )‐one ( 2 ) in Me 2 NCHO in the presence of KOH. More conveniently, complexes of 1 can be prepared in situ by the reaction of 2 with a ruthenium(II) complex of 3 in the presence of K 2 CO 3 . This methodology has been developed for the synthesis of a range of mono‐, di‐, tri‐ and hexanuclear complexes with a variety of Xtpy (Xtpy = 4′‐substituted 2,2′:6′,2″‐terpyridine) terminator ligands. The molecular structure of 1 ( a = 9.623(2), b = 11.241(1), c = 11.828(1) Å; space group P 1 ; α = 93.064(9), β = 107.072(14), γ = 99.088(14)°; Z = 2, R = 0.0450, R w = 0.0577) has been determined. The generality of the methodology may ultimately be limited by the sensitivity of the ether‐linkage in 1 to attack by nucleophiles.