Copper corroles are of interest for their ability to catalyze reactions such as the hydrogen evolution reaction and oxygen reduction reactions, but also for use in medicinal purposes. The copper corrole has also drawn significant attention due to its unique multiconfigurational electronic structure which leads to a saddled geometry in the ground state. Although the ground state of the copper corrole has a saddled geometry, the structure of the first excited state is planar. Specifically, tris-meso substituted copper corroles have played a significant role in catalysis. By performing CASPT2 geometry optimizations using both electron donating (-OH, -OCH3, -CH3) and electron withdrawing (-CF3, NO2, -CN) groups, the impact of the functional group on the structure and relative energies of the lowest singlet and triplet states is explored. The CASPT2 geometry was optimized with a minimal active space (4e,5o) showing that the saddling increases from electron donating to withdrawing groups in the singlet (S0) ground state. In DFT, the same trend is observed, although the magnitude of the change in saddling is more prominent. The electronic structure is then further studied on the CASPT2 optimized structure for all of the functionalized corroles using a larger active space. The effect of ligand functionalization on the electronic structure, energy splitting between the ground singlet and first excited state, ground-state singlet and lowest triplet state will be discussed.

Electronic structure and molecular geometry of tris-meso substituted copper corroles

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