Table 3. ET Kinetic Data: Related Data and Calculated Reaction Constants from Time-Resolved Spectroscopies in Degassed CH3CN Solutionsa.
| fluorescence
quenching |
TAS |
Tr-XAS |
||||||
|---|---|---|---|---|---|---|---|---|
| PS | τ0 (ns) | kq(BIH) (× 109 M–1 s–1) | ηq | τ0′ (ns) | τ1 (μs) | kET (× 108 M–1 s–1) | τ0″ (ns) | τ2 (μs) |
| CuBCP | 289 ± 5 | 9.35 ± 0.55 | 99.3 ± 0.2% | 302 ± 13 | 75.8 ± 5.2 | 3.72 ± 0.51 | 287 ± 63 | 27.6 ± 2.6 |
| CuPBCP | 33.0 ± 3.1 | 20.7 ± 1.1 | 97.2 ± 1.1% | 47.0 ± 6.2 | 234 ± 26 | 4.77 ± 0.92 | 37.0 ± 9.0 | 6.01 ± 2.83 |
| CuPPBCP | 206 ± 4 | 10.3 ± 0.6 | 99.1 ± 0.4% | 214 ± 10 | 280 ± 36 | 5.47 ± 0.85 | 191 ± 40 | 4.40 ± 1.86 |
a
Errors are provided as the standard deviation from three parallel experimental data. τ0: excited-state lifetime measured by time-resolved luminescence spectroscopy. kq(BIH).: reductive quenching rate constant with BIH from fluorescence quenching. ηq: quenching fractions with BIH ([BIH] = 0.05 M) from fluorescence quenching. τ0′: excited-state lifetime measured by TAS. τ1: reduced-state lifetime measured by TAS. kET.: reaction rate constant between reduced PS and CoTCPc determined by TAS. τ0″: excited-state lifetime measured by tr-XAS. τ2: formation time scales for the Co(I) species measured by tr-XAS.