Table 3. Summary of various DFT calculated orbital compositions (percent Ni/Co/S contribution per hole) using the def2-TZVP basis set and PCM(CH₃CN) condensed-phase model from the AIM analyses of the [Ni(TU)₆]²⁺ and [Co(TU)₄]²⁺ complexes.

		Ni†	S	Co‡	S
GGA (BP86) ‘Rung 2’	LUMO+2 (Co 3d xy )	–	–	66	24
	LUMO+1 (Ni 3d z 2 or Co 3d yz )	60	30	44	18
	LUMO (Ni 3d_{x^{2} - y^{2}} or Co 3d xz )	58	34	72	20
	Average for all electron holes	59	32	61	21
	Ratio of Ni/Co S character §	1.52
metaGGA (TPSS) ‘Rung 3’	LUMO+2 (Co 3d xy)	–	–	69	22
	LUMO+1 (Ni 3d z 2 or Co 3d yz )	63	26	58	19
	LUMO (Ni 3d_{x^{2} - y^{2}} or Co 3d xz )	62	30	57	16
	Average for all electron holes	63	29	61	19
	Ratio of Ni/Co S character §	1.52
hybrid GGA (B3LYP) ‘Rung 4’	LUMO+2 (Co 3d xy)	–	–	44	19
	LUMO+1 (Ni 3dz2 or Co 3dyz)	66	21	73	16
	LUMO (Ni 3dx2-y2 or Co 3dxz)	66	25	27	18
	Average for all electron holes	66	23	48	18
	Ratio of Ni/Co S character §	1.28

^†Two 3d electron holes.

^‡Three 3d electron holes.

^§Experimental ratio from S K-XANES (Table 2 ▸) is 2.3–2.5.