title: Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy
metadata.name: dc.contributor.author
metadata.value: Mereshchenko, Andrey S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Olshin, Pavel K
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Myasnikova, Olesya S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Panov, Maxim S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kochemirovsky, Vladimir A
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Skripkin, Mikhail Yu
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Moroz, Pavel N
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Zamkov, Mikhail
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Tarnovsky, Alexander N
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-08T08:50:11Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-08T08:50:11Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2016-03-24
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.1021/acs.jpca.5b12509
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 10.1021/acs.jpca.5b12509
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1979
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: 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) solvatocomplexes 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.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy
metadata.lang: en_GB
resources.filename: JPCA2016_Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/1979/1/JPCA2016_Ultrafast%20Photochemistry%20of%20Copper%28II%29%20Monochlorocomplexes%20in%20Methanol%20and%20Acetonitrile.pdf
resources.format: Adobe PDF
resources.size: 3,84 MB