Indexed on: 14 Feb '17Published on: 14 Feb '17Published in: Chemical Reviews
Presented herein is a comprehensive account of the electronic structure of corrole derivatives. Our knowledge in this area derives from a broad range of methods, including UV-vis-NIR absorption and MCD spectroscopies, single-crystal X-ray structure determination, vibrational spectroscopy, NMR and EPR spectroscopies, electrochemistry, X-ray absorption spectroscopy, and quantum chemical calculations, the latter including both density functional theory and ab initio multiconfigurational methods. The review is organized according to the Periodic Table, describing free-base and main-group element corrole derivatives, then transition-metal corroles, and finally f-block element corroles. Like porphyrins, corrole derivatives with a redox-inactive coordinated atom follow the Gouterman four-orbital model. A key difference from porphyrins is the much wider prevalence of noninnocent electronic structures as well as full-fledged corrole(•2-) radicals among corrole derivatives. The most common orbital pathways mediating ligand noninnocence in transition-metal corroles are the metal(dz2)-corrole("a2u") interaction (most commonly observed in Mn and Fe corroles) and the metal(dx2-y2)-corrole(a2u) interaction in coinage metal corroles. Less commonly encountered is the metal(dπ)-corrole("a1u") interaction, a unique feature of formal d(5) metallocorroles. Corrole derivatives exhibit a rich array of optical properties, including substituent-sensitive Soret maxima indicative of ligand noninnocence, strong fluorescence in the case of lighter main-group element complexes, and room-temperature near-IR phosphorescence in the case of several 5d metal complexes. The review concludes with an attempt at identifying gaps in our current knowledge and potential future directions of electronic-structural research on corrole derivatives.