Karl M. Kadish

Analytical Chemistry. Chemistry and electrochemistry of compounds of biological interest; porphyrin chemistry, spectroelectrochemistry; redox reactions of transition metal complexes; electrochemistry of metal-metal bonded complexes, organometallic chemistry, fullerene chemistry and fullerene electrochemistry.

One area of our research involves the chemistry and electrochemistry of metalloporphyrins and related macrocycles. Work in our laboratory is oriented towards an elucidation of the redox properties of metalloporphyrins and metallocorroles containing both main group and transition metal ions. The general approach has been to study the redox potentials and electron transfer mechanisms as a function of solvent and supporting electrolyte, type and oxidation state of central metal ion, axial coordination of the metal ion and macrocycclic structure. Special emphasis has been place on the use of cyclic voltammetry and spectroelectrochemistry but a large number of other electrochemical and spectroscopic methodologies are also utilized.

In this regard, we have developed and expanded the use of thin-layer spectroelectrochemical techniques involving FTIR, ESR and UV-visible methods, and a number of projects involve the application of these techniques towards the solving of chemical problem. The UV-visible and near-IR measurements are carried out using diode array spectrophotometers and this allows for a rapid acquisition of data which is then used in elucidating both kinetic and thermodynamic aspects of the various electron transfer reactions.

Research is also in progress to elucidate the redox reactions of different dirhodium and diruthenium complexes with bridging anionic ligands. The numerous redox reactions of these compounds are investigated by several electrochemical techniques and the products of each electrode reaction are characterized by ESR, FTIR and/or thin layer spectroelectrochemistry.

Finally, our most recent project involves the chemistry and electrochemistry of fullerenes, organofullerenes and metallofullerene derivativess. The C₆₀ molecule can be reduced by up to six electrons and a rich reductive electrochemistry is also observed for many organofullerene and metallofullerene derivatives. Each electrogenerated fullerene has a different chemistry and these anionic compounds are being investigated by chemical, electrochemical and spectroscopic methods under a variety of solution conditions as well as in the solid state.