Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 120, Issue 11, Pages 1833-1844Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b12509
Keywords
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Funding
- Saint-Petersburg State University [12.50.1189.2014, 12.42.1270.2014]
- NSF CAREER [CHE-0847707]
- NSF MRI [CHE-0923360]
- RFBR [14-03-01003, 15-03-05139, 16-33-00646]
- NSF Award [CHE-1465052]
- Saint Petersburg State University research [12.38.219.2015]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1465052] Funding Source: National Science Foundation
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Photochemistry of copper(II) monochlorocomplexes in methanol and acetonitrile solutions is studied by UV-pump/broadband deep-UV-to-near-IR probe femtosecond transient absorption spectroscopy. Upon 255 and 266 nm excitation, the complexes in acetonitrile and methanol, respectively, are promoted to the excited ligand-to-metal charge transfer (LMCT) state, which has a short (sub-250 fs) lifetime. From the LMCT state, the complexes decay via internal conversion to lower-lying ligand field (LF) d-d excited states or the vibrationally hot ground electronic state. A minor fraction of the excited complexes relaxes to the LF electronic excited states, which are relatively long-lived with lifetimes >1 ns Also, in methanol solutions, about 3% of the LMCT-excited copper(II) monochlorocomplexes dissociate forming copper(I) solvato complexes and chlorine atoms, which then further react forming long-lived photoproducts. In acetonitrile, about 50% of the LMCT-excited copper(II) monochlorocomplexes dissociate forming radical and ionic products in a ratio of 3:2. Another minor process observed following excitation only in methanol solutions is the re-equilibration between several forms of the copper(II) ground-state complexes present in solutions. This re-equilibration occurs on a time scale from sub-nanoseconds to nanoseconds.
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