Table 4. Selected Singlet and Triplet Excited States Calculated at the TDDFT B3LYP/(def2-SVP + LANL2DZ) Level for Complex 2+ in DMSO Solutiona.
| complex | state | energy (eV) | λ (nm) | f.osc. | monoexcitations | nature | description |
|---|---|---|---|---|---|---|---|
| 2 | S1 | 2.200 | 563.6 | 0.0004 | HOMO → LUMO (85) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT |
| S2 | 2.228 | 556.4 | 0.0036 | HOMO → LUMO + 1 (67) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT | |
| S3 | 2.252 | 550.6 | 0.0212 | HOMO– 1 → LUMO (70) | dπ(Ru) → π*phen | 1MLCT | |
| HOMO– 1 → LUMO + 1 (15) | dπ(Ru) → π*phen | 1MLCT | |||||
| S4 | 2.324 | 533.4 | 0.0140 | HOMO → LUMO + 1 (16) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT | |
| HOMO → LUMO + 2 (44) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT | |||||
| HOMO → LUMO + 3 (25) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT | |||||
| S5 | 2.338 | 530.4 | 0.0059 | HOMO– 1 → LUMO + 1 (42) | dπ(Ru) → π*phen | 1MLCT | |
| HOMO → LUMO + 2 (39) | dπ(Ru) + πsal → π*phen | 1MLCT/1LLCT | |||||
| S11 | 2.717 | 456.4 | 0.1146 | HOMO– 2 → LUMO (49) | dπ(Ru) → π*phen | 1MLCT | |
| HOMO– 1 → LUMO + 3 (15) | dπ(Ru) → π*phen | 1MLCT | |||||
| S13 | 2.930 | 423.2 | 0.1501 | HOMO– 2 → LUMO (17) | dπ(Ru) → π*phen | 1MLCT | |
| HOMO– 2 → LUMO + 1 (29) | dπ(Ru) → π*phen | 1MLCT | |||||
| HOMO– 2 → LUMO + 3 (19) | dπ(Ru) → π*phen | 1MLCT | |||||
| HOMO– 1 → LUMO + 2 (15) | dπ(Ru) → π*phen | 1MLCT | |||||
| T1 | 1.853 | 669.1 | HOMO– 1 → LUMO (41) | dπ(Ru) → π*phen | 3MLCT | ||
| HOMO → LUMO (25) | dπ(Ru) + πsal → π*phen | 3MLCT/3LLCT | |||||
| HOMO → LUMO + 1 (19) | dπ(Ru) + πsal → π*phen | 3MLCT/3LLCT | |||||
| T2 | 1.909 | 649.5 | HOMO → LUMO (16) | dπ(Ru) + πsal → π*phen | 3MLCT/3LLCT | ||
| HOMO → LUMO + 1 (49) | dπ(Ru) + πsal → π*phen | 3MLCT/3LLCT | |||||
| T3 | 1.991 | 622.7 | HOMO → LUMO + 1 (18) | dπ(Ru) + πsal → π*phen | 3MLCT | ||
| HOMO → LUMO + 4 (73) | dπ(Ru) + πsal → π*sal | 3MLCT/3LC |
a
Vertical excitation energies (E), dominant monoexcitations with contributions (within parentheses) of >15%, the nature of the electronic transition, and the description of the excited state are summarized.