Table 1. Photophysical and Calculated Properties of (Aza)heptacenes.

compd	λabs ona [nm]	λabs maxb [nm]	Eg measc/Eg cald [eV]	E1/2red1e [V]	EAf/ELUMOg [eV]	IPh/EHOMOg [eV]
Hep	950	865	1.30/1.22	–1.15	–3.65/-3.43	–4.95/-4.65
DAH1	1074	957	1.15/1.17	–0.72	–4.08/-3.71	–5.23/-4.88
DAH2	1064	917	1.17/1.19	–0.77	–4.03/–3.70	–5.20/–4.89
TAH	1152	1011	1.08/1.12	–0.69	–4.11/–4.02	–5.19/–5.14
HAH	1045	961	1.19/1.19	–0.60	–4.20/–4.19	–5.39/–5.38

^aOnset of the lowest energy absorption maxima.

^bMost intense absorption of the p-band.

^cOptical gap calculated by λ_onset.

^dHOMO–LUMO gap calculated by DFT calculation.

^eFirst reduction potentials measured by cyclic voltammetry in DCM against Fc/Fc⁺ as the internal standard (−4.80 eV) using a Pt working electrode and Bu₄NPF₆ as electrolyte.

^fElectron affinities (EA) estimated from first reduction potentials; EA = −4.80 eV – E_red.⁴³

^gFMO values calculated by DFT calculation⁴⁴ (Gaussian16 B3LYP, def2TZVP; TMS groups were used instead of TIPS).

^hIonization potential (IP) = EA – E_g meas.