Expanded ligands: bis(2,2′:6′,2″-terpyridine carboxylic acid)ruthenium(ii) complexes as metallosupramolecular analogues of dicarboxylic acids

Abstract

Ligands in which multiple metal-binding domains are linked by a metal-containing moiety rather than a conventional organic group are described as “expanded ligands”. The use of 4,4′-difunctionalised {Ru(tpy)₂} units provides a linear spacer between metal-binding domains and we have extended this motif to expanded ligands containing two carboxylic acid metal-binding domains. In this paper, we describe the synthesis and structural characterisation of ruthenium(II) complexes of 2,2′:6′,2″-terpyridine-4′-carboxylic acid and 4′-carboxyphenyl-2,2′:6′,2″-terpyridine. The ability of the ruthenium(II) centre to charge compensate deprotonation of the carboxylic acid leads to Zwitterionic complexes and three representative compounds have been structurally characterised.