. Author manuscript; available in PMC: 2020 Feb 21.

Published in final edited form as: J Phys Chem B. 2019 Feb 6;123(7):1578–1591. doi: 10.1021/acs.jpcb.8b11982

Table 2.

Photochemical kinetics of Re126FWCu at ~1 mM concentration.^a

Cu^II	Cu^I	Underlying processes
8 ps	5 ps	CT relaxation^b and small CS rise
530 ps	670 ps	CT relaxation^b and decay; CS rise
14 ns	6–8 ns	CT relaxation^b and decay; CS rise
63 ns		CT and CS decay; bleach recovery
	70–90 ns	CT and very small CS decay; bleach recovery
	1.2–2.1ns	RP (CS)^c decay and bleach recovery
>1 μS	>10 μs	very weak residual CS decay and bleach recovery

Time constants were obtained by global fitting of pico- and nanosecond TRIR spectra obtained in several independent experiments. Characters of underlying processes were inferred from the evolution- and decay associated spectra (Figures 4, 5).

Relaxation is manifested by dynamic shifts of the CT bands and a derivative-like shape of the corresponding DAS features.

RP spectral features cannot be distinguished from those of CS (LCS, HCS).