DFT calculations on manganese(III)5,10,15-tris(pentafluorophenyl)-corrole

Geometries of manganese (III) 5,10,15-tris(pentafluorophenyl) corrole (TPFC)Mn-III and its imidazole axial binding adduct (TPFC)Mn-III(Im) were optimized by using DFT(UB3LYP) method at 6-31G{*} basis set level. Calculation results indicated that (TPFC)Mn-III and (TPFC)Mn-III(Im) had the same spin state (s=2) in their ground states. (TPFC) Mn-III had a plane structure, while Mn atom in (TPFC)Mn-III(Im) was above the corrole N-4 mean plane 0.02734 nm. NBO analysis showed that the electronic configuration of central Mn atom in (TPFC)Mn-III and (TPFC)Mn-III(Im) was (d(xz))(1)(dyz)(1)(d(z2))(1)(d(x2-y2))(1) (d(xy))(0). The energies of frontier orbitals of (TPFC)Mn-III(Im) were significantly higher than those of (TPFC)Mn-III, and the Mn-imidazole d-p pi bonding could be found from beta-(LUMO+3) obital of (TPFC.)Mn-III (Im). In addition, electronic spectra of (TPFC)Mn-III and (TPFC)Mn-III(Im) were calculated by using TD-UB3LYP/6-31G{*} method, and it could be found that Q band had more "four-orbital" characters than B band. CT band of (TPFC)Mn-III was mainly contributed from,beta-(HOMO-1) to beta-(LUMO+5) and beta-HOMO to beta-(LUMO+4) transitions, and CT band of (TPFC)Mn-III(Im) was mainly contributed from beta-(HOMO-1) to beta-(LUMO+3) and beta-HOMO to beta-(LUMO+4) transitions