Pure and Applied Chemistry · 1984 · 93 citations · 0 references
Natural SciencesChemistryInorganic ChemistryMaterials ChemistryOrganometallic ChemistryChemical BondingCluster ChemistryCluster CompoundsCoordination ChemistryMetal-ligand BondingTransition Metal ComplexesElectron TransferElectron Transfer RatesElectronic Structure Of Metal ComplexesMetal Ion ChemistryMetal Ion Redox ChemistryMetal Ligand CoordinationMetal-organic FrameworksPhotochemical Oxidation
This paper reviews some of the more interesting and recent phenomena associated with the metal ion cage chemistry involving hexaazamacropolycycles. Synthetic aspects are addressed in relation to making cages with smaller and larger hole sizes in order to modulate redox potentials and electron transfer rates. The introduction of substituents is also examined in relation to these factors along with the effect of ligand geometry and strain. Relevant redox potentials, spectroscopic and photochemical properties of the different metal ion cages are displayed. Aspects of the synthesis of dimer complexes and some properties of the dimer complexes are outlined. The route whereby the metal is extruded from the cage in acid conditions is examined in some detail for the Cusar2 ion. The properties of an extraordinarily stable zinc alkyl cage are examined and finally various prospects for the use of the metal ion cages are reviewed.