Table 2. TD-DFT-calculated photophysical data for 1 and 5 at the CAM-B3LYP/6-31G(d) level in hexane a .
| Transition (f) | E/eV b | λ/nm b | Dominant components c | |
| 1 | S1 ← S0 (0.054) | 3.50 (3.16) | 354 (392) | LUMO+1 ← HOMO–1 (44%), LUMO ← HOMO (38%) |
| S2 ← S0 (0.736) | 3.50 (3.16) | 354 (392) | LUMO ← HOMO–1 (38%), LUMO+1 ← HOMO (44%) | |
| S3 ← S0 (1.496) | 3.70 (3.33) | 335 (372) | LUMO ← HOMO–4 (11%), LUMO+1 ← HOMO–3 (29%), LUMO ← HOMO–2 (37%) | |
| S5 ← S0 (0.778) | 4.19 (3.78) | 296 (328) | LUMO ← HOMO–4 (55%), LUMO+1 ← HOMO–3 (15%) | |
| 5 | S1 ← S0 (1.739) | 2.31 (2.23) | 537 (554) | LUMO ← HOMO (94%) |
| S2 ← S0 (0.294) | 3.35 (3.20) | 370 (388) | LUMO ← HOMO–2 (33%), LUMO+1 ← HOMO–2 (20%), LUMO+2 ← HOMO–2 (27%), LUMO+3 ← HOMO–2 (10%) | |
| S4 ← S0 (0.260) | 3.38 (3.20) | 367 (388) | LUMO ← HOMO–1 (28%), LUMO+1 ← HOMO–1 (24%), LUMO+2 ← HOMO–1 (26%), LUMO+3 ← HOMO–1 (13%) |
aTransitions with modest to high oscillator strength f are displayed in this table. Others are shown in the ESI.
bValues in parentheses are experimental absorption maxima in hexane.
cComponents with greater than 10% contribution shown. Percentage contribution approximated by 2 × (ci)2 × 100%, where ci is the coefficient for the particular ‘orbital rotation’.