Large coordination complexes: synthesis, characterisation and properties

Two aspects of the chemistry of polynuclear complexes are discussed. The first part concerns the application of electrospray mass spectrometry to such complexes. The concept of pseudoisotopic molecules is introduced as two chemical entities which have similar chemical behaviour but which differ in mass and may thus be distinguished in the mass spectrum. It is shown how mixtures of pseudoisotopes readily allow the identification of the nuclearity of complexes. Studies of the exchange of pseudoisotopes show surprising variations in labilty. In favorable cases the evolution of the mass spectrum yields information on the mechanism of the assembly. In the second part we discuss a strategy for the synthesis of large molecular cages, based on the fullerene topology, but using coordinative bonding to assemble the structure.