Toward Reliable DFT Investigations of Mn-Porphyrins through CASPT2/DFT Comparison.

The low-energy spectroscopies of Mn(II) and Mn(III) porphyrin (P) complexes were investigated using complete active space and subsequent perturbative treatment (CASPT2) as well as DFT-based calculations. Starting from DFT optimizations of Mn(II)P and Mn(III)PCl using crystallographic data, the CASPT2 results show that whatever the relative position of the Mn(II) ion with respect to the porphyrin cavity, the high-spin state S = 5/2 of the [MnP] unit lies much lower in energy than the intermediate S = 3/2 state. Not only are these results in agreement with experimental observations but they also differ from previous theoretical conclusions. In the Mn(III) complexes, σ and π charge redistributions compete to result in a S = 2 ground state. The performances of different functionals have been tested in the reproduction of the CASPT2 spin gaps. Our results confirm that the Mn(II) system is very challenging, as GGA functionals fail in the spin states ordering and in the reproduction of the gaps, unless a high percentage of exact HF exchange (55%), as in KMLYP, is incorporated. This inspection demonstrates the need for specific active space functional to investigate the low-energy spectroscopy of [MnP] units.