Table 2. Emission Properties of Complexes 3–8a.
| complex | HOMO (eV) | LUMO (eV) | HLG (eV) | calc λema (nm) | media (T, K) | λem (nm) | τobs (μs) | Φ | krb (s–1) | knrb (s–1) | kr/knr |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 3 | PMMA (298) | 599 | 1.5 | 0.01 | 6.6 × 103 | 6.6 × 105 | 0.01 | ||||
| –4.81 | –1.27 | 3.54 | 591 | MeTHF (298) | 614 | 2.3 | 0.01 | 4.3 × 103 | 4.3 × 105 | 0.01 | |
| MeTHF (77) | 578 | 4.1 | |||||||||
| 4 | PMMA (298) | 593 | 3.1 | 0.02 | 6.4 × 103 | 3.1 × 105 | 0.02 | ||||
| –4.75 | –1.24 | 3.51 | 602 | MeTHF (298) | 610 | 3.1 | 0.02 | 6.4 × 103 | 3.1 × 105 | 0.02 | |
| MeTHF (77) | 550 | 5.2 | |||||||||
| 5 | PMMA (298) | 593 | 3.3 | 0.01 | 3.0 × 103 | 3.0 × 105 | 0.01 | ||||
| –4.78 | –1.29 | 3.49 | 564 | MeTHF (298) | 611 | 2.7 | 0.01 | 3.7 × 103 | 3.6 × 105 | 0.01 | |
| MeTHF (77) | 574 | 3.4 | |||||||||
| 6 | PMMA (298) | 562, 599 | 4.4 | 0.03 | 6.8 × 103 | 2.2 × 105 | 0.03 | ||||
| –4.58 | –1.11 | 3.47 | 577 | MeTHF (298) | 562 | 3.9 | 0.02 | 5.1 × 103 | 2.5 × 105 | 0.02 | |
| MeTHF (77) | 546, 592 | 3.9 | |||||||||
| 7 | PMMA (298) | 570, 611 | 3.7 | 0.06 | 1.6 × 104 | 2.5 × 105 | 0.06 | ||||
| –4.50 | –1.08 | 3.42 | 596 | MeTHF (298) | 627 | 4.5 | 0.03 | 6.6 × 103 | 2.1 × 105 | 0.03 | |
| MeTHF (77) | 559, 620 | 3.5 | |||||||||
| 8 | PMMA (298) | 598, 658, 728 | 2.7 | 0.03 | 1.1 × 104 | 3.6 × 105 | 0.03 | ||||
| –4.35 | –1.09 | 3.26 | 620 | MeTHF (298) | 602, 651 | 1.5 | 0.08 | 5.3 × 104 | 6.1 × 105 | 0.08 | |
| MeTHF (77) | 584, 641, 708 | 3.3 |
a
Predicted from TD-DFT calculations in THF at 298 K by estimating the energy difference between the optimized T1 and singlet S0 state.
b
Calculated according to the equations kr = Φ/τobs and knr = (1 – Φ)/τobs, where kr is the radiative rate constant, knr is the nonradiative rate constant, Φ is the quantum yield, and τobs is the excited-state lifetime.