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Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways.

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Title: Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways.
Authors: Mereshchenko, Andrey S.1,2 andreym@chem.spbu.ru, Olshin, Pavel K.1, Karimov, Artur M.1, Skripkin, Mikhail Yu.1, Burkov, Kim A.1, Tveryanovich, Yury S.1, Tarnovsky, Alexander N.2,3
Source: Chemical Physics Letters. Nov2014, Vol. 615, p105-110. 6p.
Subjects: Photochemistry, Copper ions, Metal complexes, Photoreduction, Dissociation (Chemistry)
Abstract: Photochemistry of [Cu(MeCN) 3 Cl] + , [Cu(MeCN)Cl 3 ] − , and [CuCl 4 ] 2− copper(II) chlorocomplexes in acetonitrile solution is studied by means of the combination of the steady-state photolysis and ultrafast transient absorption methods. The main relaxation pathways of the initially excited ligand-to-metal charge transfer states are internal conversion to the ground state, ionic dissociation without (photo)reduction of copper(II), and radical dissociation with (photo)reduction of copper(II). The copper(II)-to-copper(I) photoreduction quantum yields obtained from steady-state photolysis correlate with ultrafast spectroscopy data. The presence of oxygen does not affect the photoreduction quantum yields, which do not exceed 7% for the complexes studied and decrease in the series: [Cu(MeCN) 3 Cl] + > [Cu(MeCN)Cl 3 ] − > [CuCl 4 ] 2− . [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:Photochemistry of [Cu(MeCN) 3 Cl] + , [Cu(MeCN)Cl 3 ] − , and [CuCl 4 ] 2− copper(II) chlorocomplexes in acetonitrile solution is studied by means of the combination of the steady-state photolysis and ultrafast transient absorption methods. The main relaxation pathways of the initially excited ligand-to-metal charge transfer states are internal conversion to the ground state, ionic dissociation without (photo)reduction of copper(II), and radical dissociation with (photo)reduction of copper(II). The copper(II)-to-copper(I) photoreduction quantum yields obtained from steady-state photolysis correlate with ultrafast spectroscopy data. The presence of oxygen does not affect the photoreduction quantum yields, which do not exceed 7% for the complexes studied and decrease in the series: [Cu(MeCN) 3 Cl] + > [Cu(MeCN)Cl 3 ] − > [CuCl 4 ] 2− . [ABSTRACT FROM AUTHOR]
ISSN:00092614
DOI:10.1016/j.cplett.2014.10.016