Table 1.
λ abs [nm (ε, 103 m −1 cm−1)] a) | λ em [nm] b) | τ obs [µs] c) | Φ d) | E ox (V vs SCE) e) | E red (V vs SCE) f) | k r TADF (105 s−1) g) | k nr (105 s−1) h) | ΔE S1−T1 (meV) i) | k ISC (108 s−1) j) | k rISC (108 s−1) k) | |
---|---|---|---|---|---|---|---|---|---|---|---|
[Au(DippPZI)(ACD)] | 462 (7.2) | 533 | 0.32 | 0.84 | 1.05 | −1.49 | 26 | 5.0 | 40 | 21 | 6.6 |
[Au(DippPZI)(Cz)] | 475 (9.8) | 553 | 0.32 | 0.87 | 0.84 | −1.62 | 27 | 2.4 | 55 | 22 | 4.5 |
[Au(DippPZI)(DPA)] | 549 (6.6) | 663 | 0.30 | 0.26 | 0.50 | −1.58 | 8.7 | 25 | 49 | 7.9 | 1.5 |
[Au(DippPZI)(DPAC)] | 560 (9.4) | 666 | 0.26 | 0.22 | 0.54 | −1.54 | 8.5 | 30 | 64 | 25 | 2.6 |
[Au(DippPZI)(DMAC)] | 590 (6.2) | 705 | 0.16 | 0.10 | 0.39 | −1.54 | 6.3 | 56 | 52 | 3.8 | 4.7 |
[Au(DippPZI)(PXZ)] | 619 (5.6) | 750 | 0.019 | N.D. l) | 0.25 | −1.49 | N.D. l) | N.D. l) | N.D. l) | N.D. l) | N.D. l) |
Absorption peak wavelengths recorded for 10 µm Au(I) complex in deaerated toluene at 298 K;
Photoluminescence peak wavelengths recorded for Zeonex thin films doped with 5 wt % Au(I) complexes (quartz substrates) at 298 K;
Weighted average photoluminescence lifetime determined through triexponential decay fits of the photoluminescence decay traces monitored at emission peak wavelengths of Zeonex thin films doped with 5 wt % Au(I) complexes (quartz substrates) after pulsed laser excitation under 377 nm (time resolution: 32 ps);
Photoluminescence quantum yields of Zeonex thin films doped with 5 wt. % Au(I) complexes (quartz substrates) determined absolutely by integrating over a sphere at 298 K;
Oxidation;
reduction potentials determined by cyclic and differential pulse voltammetry for anhydrous THF containing 2.0 mm samples and 0.10 m TBAPF6. A Pt working and a Pt counter electrodes, and an Ag/AgNO3 pseudo reference electrode were employed. Scan rate = 0.10 V s−1 (cyclic voltammetry) and 0.004 V s−1 (differential pulse voltammetry);
Radiative decay rate of TADF emission, k r TADF = Φ /τ obs;
Nonradiative decay rate, k nr = (1 − Φ) /τ obs;
Energy difference between the S1 and T1 states determined through Boltzmann fitting of variable‐temperature τ obs values (see Figures S10 and S11, Supporting Information);
Rate constant for intersystem crossing computed from Equation S5 (Supporting Information);
Rate constant for reverse intersystem crossing computed from Equation S4 (Supporting Information);
Not determined due to weak emission.