Table 3. Selected DFT Parameters.

	bond distance (Å)b				Löewdin charge		Mulliken population (%)
model	Ni−N1(2)	Ni−N3(4)	Ni−O	Ni−S/C	Ni	F430c	Ni(3dz2+3dx2−y2)d	Ni(3dxz+3dyz)e
MCRred1a	1.99 (1.99)	2.15 (2.06)	2.25	−	0.21	−0.30	54	72
MCRred1−silent	2.06 (2.06)	2.12 (2.12)	2.26	2.44	0.22	−0.12	141	−
MCRMe	2.04 (2.02)	2.20 (2.10)	2.32	2.00	0.32	0.26	150	−

^aThe calculations were performed on simplified models (shown in Figure 6).

^bThe numbering of the Ni−N bonds is explained in Figure S2 of the Supporting Information.

^cThe charge on the entire corphin ring.

^dThe combined contribution of the antibonding Ni 3d_x²−y² and 3d_z² to the valence orbitals. In the case of MCR_red1, only 3d_x²−y² character is present.

^eValence Ni 3d_yz and 3d_xz character due to back-bonding with filled π^∗-type F₄₃₀ orbitals.