Table 6. Reduction Potentials of PFAFs^a.

compound	ref	gapb	E(LUMO)b	E1/2(0/−)	E1/2(1−/2–)	E1/2(2−/3–)	solventc
C60	(104)	1.639	–4.379	0.00	–0.40	–0.85	DCM
	(104)			0.00	–0.39	–0.85	oDCB
	(104)			0.00	–0.41		PhCN
C60(CF2)	(187)			0.15	–0.19	–0.79	oDCB
C60(CF2)2	(187)			0.14	–0.20	–0.80	oDCB
60-2-1	(104)	1.430	–4.592	0.15	–0.30	–0.80	DCM
	(104)			0.13	–0.28	–0.81	oDCB
	(104)			0.13	–0.32		PhCN
60-2-1-C2F5	(104)	1.431	–4.599	0.17	–0.24	–0.78	DCM
	(104)			0.13	–0.30	–0.82	oDCB
	(104)			0.13	–0.31		PhCN
60-2-1-n-C3F7	(104)	1.427	–4.598	0.13	–0.28	–0.82	DCM
	(104)			0.13	–0.29	–0.82	oDCB
	(104)			0.13	–0.30		PhCN
60-2-1-i-C3F7	(104)	1.435	–4.589	0.14	–0.29	–0.82	DCM
	(104)			0.13	–0.31	–0.83	oDCB
	(104)			0.10	–0.36		PhCN
60-2-1-n-C4F9	(104)	1.425	–4.607	0.11	–0.31	–0.84	DCM
	(104)			0.13	–0.30	–0.83	oDCB
	(104)			0.14	–0.30		PhCN
60-2-1-s-C4F9	(104)	1.434	–4.595	0.14	–0.29	–0.83	DCM
	(104)			0.11	–0.32	–0.85	oDCB
	(104)			0.10	–0.36		PhCN
60-2-1-n-C8F17	(104)	1.425	–4.609	0.15	–0.27	–0.81	DCM
	(104)			0.12	–0.30	–0.82	oDCB
	(104)			0.13	–0.34		PhCN
60-4-1	(5)	1.443	–4.682	0.17	–0.26	–1.01	DCM
60-4-4-i-C3F7	(94)	1.242	–4.786	0.32	–0.32	–0.80	oDCB
60-4-5-i-C3F7	(94)	1.444	–4.680	0.20	–0.26	–0.78	oDCB
60-6-1	(5)	1.445	–4.796	0.26	–0.28	–0.93	DCM
60-6-2	(5)	1.859	–4.378	–0.07	–0.53	–1.02	DCM
C59N-5	(158)	1.872	–4.374	–0.05	–0.54		DCM
60-6-3-i-C3F7	(94)	1.369	–4.830	0.32	–0.32	–0.80	oDCB
60-6-5-i-C3F7	(94)	1.461	–4.735	0.32	–0.32	–0.80	oDCB
60-6-8-i-C3F7	(94)	1.187	–4.900	0.32	–0.32	–0.80	oDCB
60-8-1	(5)	1.498	–4.850	0.33	–0.19	–0.66	DCM
60-8-2	(5)	1.482	–4.912	0.32	–0.19	–0.79	DCM
60-8-3	(5)	1.333	–5.017	0.45	–0.03	–0.96	DCM
60-8-4	(5)	1.701	–4.585	0.06	–0.38	–1.06	DCM
60-8-5	(5)	1.420	–4.863	0.31			DCM
60-10-1	(5)	1.139	–5.129	0.57	–0.07		DCM
60-10-2	(5)	1.550	–4.894	0.32	–0.47		DCM
60-10-3	(5)	1.662	–4.754	0.17	–0.44		DCM
60-10-4	(5)	1.636	–4.529	0.07	–0.47		DCM
60-10-5	(5)	1.748	–4.638	0.12	–0.46		DCM
60-10-6	(5)	1.445	–4.922	0.33	–0.34		DCM
60-10-8	(115)	1.429	–4.904	0.28	–0.36	–0.98	oDCB
60-12-1	(5)	2.245	–4.278	–0.16			DCM
60-12-2	(5)	1.614	–4.919	0.32	–0.39		DCM
60-12-3	(5)	2.086	–4.331	–0.13	–0.59		DCM
C70	(68)	1.703	–4.315	0.00	–0.40	–0.80	DCM
				0.00	–0.37	–0.78	oDCB
open-C70(CF2)	(110)			0.15	–0.18	–0.76	oDCB
closed-C70(CF2)	(110)			0.01	–0.28	–0.75	oDCB
70-2-1	(68)	1.372	–4.697	0.28	–0.14	–0.71	DCM
70-2-1-C2F5	(116)	1.369	–4.706	0.27	–0.16	–0.73	DCM
70-2-1-i-C3F7	(94)	1.367	–4.708	0.28	–0.15	–0.79	oDCB
70-2-2	(68)	1.232	–4.533	0.12	–0.26	–0.74	DCM
70-2-2-i-C3F7	(94)	1.230	–4.528	0.10	–0.31	–0.83	oDCB
70-4-1	(68)	1.334	–4.648	0.21	–0.18	–0.77	DCM
70-4-3-i-C3F7	(94)	1.367	–4.764	0.30	–0.15	–0.64	oDCB
70-4-4-i-C3F7	(94)	1.252	–4.896	0.49	0.00	–0.77	oDCB
70-6-1	(68)	1.333	–4.731	0.30	–0.14	–0.57	DCM
70-6-2	(68)	1.304	–4.758	0.34	–0.13	–0.48	DCM
70-6-3	(68)	1.560	–4.639	0.17	–0.27		DCM
70-8-1	(68)	1.707	–4.555	0.04	–0.41	–1.04	DCM
70-8-2	(68)	1.263	–4.829	0.31	–0.21	–1.28	DCM
70-10-1	(68)	2.071	–4.351	–0.11d	–0.66		DCM
70-10-2	(68)	1.823	–4.536	–0.01	–0.50		DCM
70-10-3	(68)	1.679	–4.588	0.04	–0.41		DCM
70-10-4	(68)	1.628	–4.599	0.08	–0.48	–0.86	DCM
70-10-5	(68)	1.370	–4.813	0.28	–0.21	–1.11	DCM
70-12-1	(68)	1.700	–4.664	0.09	–0.46	–0.91	DCM
70-12-2	(68)	1.671	–4.676	0.07	–0.47	–0.98	DCM
70-12-3	(68)	1.634	–4.777	0.26	–0.37	–0.90	DCM
70-12-4	(68)	1.687	–4.774	0.25	–0.41	–0.90	DCM
Sc3N@C80		1.463	–3.907	0.00	–0.36	–1.11	oDCB
Sc-2	(188)	1.149	–4.184	0.10	–0.39	–0.88	oDCB
Sc-4-1	(93)	1.103	–4.247	0.20	–0.29	–0.77	oDCB
Sc-10-1	(93)	1.079	–4.535	0.42	–0.06	–0.85	oDCB
Sc-12-1	(93)	1.238	–4.423	0.32	–0.12	–0.72	oDCB

^aThe values for PFAF derivatives are given vs the E_1/2(0/−) of the parent non-functionalized fullerene, selected E_1/2(0/−) values vs Fe(Cp)₂^+/0 are: C₆₀, −0.98 V in DCM and −1.06 V in oDCB; C₇₀, −0.98 V in DCM, −1.06 V in oDCB; Sc₃N@C₈₀, −1.26 V in oDCB.

^bPBE/TZ2P computed value.

^cDCM = dichloromethane; oDCB = o-dichlorobenzene; PhCN = benzonitrile.

^dIrreversible.