Experimental and TDDFT calculated (ωB97XD/6-31+G(d)) absorption spectra of the radical cations of 3a˙+–3d˙+ (for further details, see ESI).
| Compounds | λ abs a (nm) | λ abs b (nm) | λ calcd c (oscillator strength) (nm) | λ calcd d (oscillator strength) (nm) | Most dominant contributions c | Most dominant contributions d |
|---|---|---|---|---|---|---|
| 3a˙+ | 621 | 765 | 640 (0.3426) | 943 (0.3097) | SOMO(A) → LUMO(A) | HOMO–2(B) → SOMO(B) |
| 3b˙+ | 616 | 766 | 637 (0.3463) | 932 (0.3019) | SOMO(A) → LUMO(A) | HOMO–1(B) → SOMO(B) |
| 3c˙+ | 612 | 776 | 639 (0.3358) | 975 (0.3301) | SOMO(A) → LUMO(A) | HOMO(B) → SOMO(B) |
| 3d˙+ | 593, 725 | 791 | 648 (0.2803) | 1085 (0.3624) | SOMO(A) → LUMO(A) | HOMO(B) → SOMO(B) |
a
Experimental absorption maximum for the localized Peri˙+ and TAA(R)˙+ mixed band in DCM at room temperature (RT).
b
Experimental absorption maximum for the delocalized (DPA(R)–Peri)˙+ band in DCM at room temperature (RT).
c
Calculated absorption maximum for the localized Peri˙+ and TAA(R)˙+ mixed band in vacuum.
d
Calculated absorption maximum for the delocalized (DPA(R)–Peri)˙+ band in vacuum.