Silver Anniversary of the Renaissance in Metallocorrole Chemistry.

The 1999 discovery of one-pot corrole synthesis opened the floodgates for research on these unique macrocyclic chelating agents. The enormous impact of this discovery has been documented in numerous reviews describing advances in the synthetic chemistry of corroles and selected applications in which corroles are key components. Our silver anniversary review focuses on the structures and reactions of all well characterized corrole-chelated d- and p-block metal complexes, including discussions of their electronic excited-state physics and chemistry. Emphasis is placed on electronic structure of the trinegative N4 coordination core, which stabilizes high-valent metals and activates low-valent ones, and, importantly, profoundly influences ground- and excited-state reactivity. Our story highlights the unique properties of corroles that have made them the molecular components of choice in a plethora of applications. These include their utility for sensing gases and anions, rescue of vital biomolecules from oxidative damage, destruction of cancerous cells, and catalysis of reactions critical for organic synthesis, as well as those involved in clean energy processes such as production of hydrogen and reduction of oxygen. In our view, research on corroles will continue to grow by leaps and bounds, most especially in areas of human health research and renewable energy science and technology.