Summary of IVCT band analysis for electrochemically generated [(^RL)₂Ni]⁺.

Compound	[(tBuL)2Ni]+	[(CF3L)2Ni]+	[(ClL)2Ni]+
E OP = λ (cm−1)	5549	5784	5711
ε max (M−1 cm−1)	15 740	14 400	4970a
Δν1/2 (cm−1)	3051	2781	3998
Δν1/2 HTL (cm−1)	3580	3627	3604
θ = Δν1/2/Δν1/2 (HTL)	0.852	0.767	1.109
d (Å)b	4.055c	4.055c	4.055c
H ab (cm−1)	2609	2432	1703
α = 2Hab/λ	0.940	0.841	0.596
ΔG* (cm−1)	4.936	36.58	232.6
k et (s−1)	2.065 × 1015	1.505 × 1015	2.859 × 1014
K com d	1.76 × 103	2.61 × 103	1.33 × 105
	Class IIB	Class IIB	Class IIBa

^aValue for extinction coefficient may be artificially low due to decomposition. See text for full discussion of implications for Class IIB vs. IIA assignment.

^bDistance (Å) between electroactive N_amido centres.

^cAverage value from DFT-optimized structure of [(^tBuL)₂Ni]⁺ [S = 3/2; SMD-uPBE0/6-31+G(d,p)]. Due to the similarities of the other complexes to [(^tBuL)₂Ni]⁺, DFT was not run for these complexes. Note: very small differences were observed between calculated bond distances of [(^tBuL)₂Ni] and [(^tBuL)₂Ni]⁺.

^d K _com = e^(ΔEF/RT), T = 295 K; k_B = 0.695 cm⁻¹ K⁻¹; h = 3.36 × 10⁻¹¹ cm⁻¹ s; T = 295 K.