Table 2.

Reactivity and magnetic indices of aromaticity of selected unsubstituted expanded porphyrins in neutral, anionic, and cationic states. A, NA, and AA stand for aromatic, nonaromatic, and antiaromatic, respectively.

π e	Δη	$\Delta E_{HL}$	Λ	NICS(0)	NICS zz (1)	AICD
26R	−1.8[a]	3.78	−153.6	−8.7	−11.7	A
26R2−	3.9	3.44	−249.6	−10.1	−23.1	A
26F2−	[b]	3.12	[b]	−12.8	−27.5	A
28R	−11.5	3.09	241.1	9.8	23.1	AA
28R2+	−8.5	3.14	272.4	8.5	33.4	AA
28M	5.3	3.85	−90.0	−7.5	−6.1	A
28M2+	7.1	3.90	−111.1	−5.9	−5.4	A
32H	−2.8	3.38	84.6	4.0	16.1	AA
32H4−	−8.1	2.60	375.3	13.4	40.4	AA
32M	4.1	3.72	−51.1	−5.4	−5.8	A
32M4−	−4.4[a]	3.00	−198.3	−5.8	−13.1	A
32M3+	2.1	3.51	−151.5	−5.3	−8.4	A
32F	−9.2	3.23	40.8	0.3	−3.8	NA
32F3+	−7.4	3.16	87.0	1.2	10.3	NA
36H a	−9.0	3.09	191.2	4.4	14.3	AA
36H b	−7.7	3.43	90.2	9.8	8.7	AA
36H ${}_a^{2-}$	−3.4	2.95	231.6	4.9	16.2	AA
36M b	0.9[a]	3.76	−53.1	−1.2	−4.5	A
36M ${}_b^{2+}$	12.9	3.43	−77.2	−1.5	−3.9	A
36F a	−7.8	3.27	8.7	−3.8	0.4	NA
38H ${}_b^{2+}$	5.3	3.23	−190.8	−3.3	−6.3	A

^[a] Due to a highly distorted methylene derivative, 26R, 32M⁴⁻ , and 36M _b exhibit negative or reduced Δη values. ^[b] The methylene isomer untwists the conformation 26F²⁻ during the optimization, precluding the evaluation of Δη and Λ. ^[c] NICS‐based index in ppm, $\Delta \eta$ in kcal ⋅ mol⁻¹, $\Delta E_{HL}$ in eV, Λ in ppm ⋅ cgs.