Four new cavitand ligands, modified at the lower rim with cyano and pyridyl
functional groups, have been synthesized and their coordinative behaviour
toward transition metal ions has been explored. The outcome of the self-ass
embly of these compounds in the presence of different metal precursors is b
iased toward the formation of intramolecular complexes, independent of the
coordination geometry imposed by the metal centre. Dimeric species have bee
n obtained by decreasing the number of ligands at the lower rim from four t
o two and by using a metal precursor capable of exchanging four ligands sim
ultaneously.