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. 2019 Jan 7;5(1):192–200. doi: 10.1021/acscentsci.8b00882

Figure 3.

Figure 3

Difference TRIR spectra of Re126WWCuI measured at selected time delays after 400 nm, 50 fs excitation. Measured in ∼1.8 mM/D2O solution, 20 mM KPi (pD ≅ 7.1). Blue and red labels denote features due to the 3CT state (*Re) and reduced ReI(H126)(CO)3(dmp•–) in the two CS states (and RP at later time delays). Negative bands correspond to depleted ground-state population. The spectral features evolve in the directions of the arrows. Time evolution of the highest CT band is largely determined by excited-state relaxation (ref (38); the simultaneous decay and rise of 3CT and CS features on late-picosecond and early nanosecond time scales confirm (ultra)fast reduction of the excited Re label. Because of the high concentration used (∼1.8 mM), the kinetics correspond to a combination of intra- and intermolecular processes.