Table S3.
CAM-B3LYP/D3/6-31G(d,p) and RICC2/Def2TZVP excitation wavelengths in nanometers (and in kcal/mol) reported for the different chromophore variants
| Compound (total charge) | CAM-B3LYP/D3/6-31G(d,p) [*6-311++G(d,p)] | RICC2/Def2TZVP |
| C(−1) (Exp.: 49.4 kcal/mol; 587 nm) | 503 (56.8) | 579 (49.4) |
| C(−1) | 514 (55.6)* | — |
| C, large(−1) | 460 (62.2) | — |
| C-H+(0) | 391 (73.1) | 404 (70.8) |
| C-H2(−1) | 409 (69.9) | 443 (64.5) |
| C_spiro(−1) | 582 (49.1) | 657 (43.5) |
| B(−1) | 390 (73.3) | 411 (69.6) |
| B(−1) | 403 (70.9)* | — |
| B, large(−1) | 351 (81.5) | — |
| B-H+(0) | 334 (85.6) | 346 (82.7) |
| B_spiro(−1) | 392 (72.9) | 419 (68.2) |
| 7_ring(sp2)(0) | 292 (97.9) | 311 (91.9) |
| 7_ring(sp3)(−1) | 413 (69.2) | 490 (58.4) |
| D(−1) | 404 (70.8) | 434 (65.9) |
| D(−1) | 414 (69.1)* | — |
| D, large (0) | 372 (76.9)† [332 (86.1)] | — |
If not otherwise noted, the small model (and appropriate modifications thereof) of Fig. S3 has been used in the calculations. Where the larger model has been used, this is indicated using the word “large.”
*
Energies obtained with a larger basis set [6-311++G(d,p)] instead of 6-31G(d,p).
†
In this case the excitation energy for the structure optimized in PCM = water was chosen, because with PCM = diethylether (excitation energy reported in brackets) an artificial change in the protein environment occurs that influences the excitation energy significantly.