Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy.
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| Title: | Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy. |
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| Authors: | Mereshchenko, Andrey S.1 a.mereshchenko@spbu.ru, Olshin, Pavel K.1, Myasnikova, Olesya S.1, Panov, Maxim S.1, Kochemirovsky, Vladimir A.1, Skripkin, Mikhail Yu.1,2, Moroz, Pavel N.3,4, Zamkov, Mikhail3, Tarnovsky, Alexander N.3,4 atarnov@bgsu.edu |
| Source: | Journal of Physical Chemistry A. Mar2016, Vol. 120 Issue 11, p1833-1844. 12p. |
| Subjects: | Photochemistry techniques, Methanol, Acetonitrile synthesis, Ligands (Chemistry), Copper compounds synthesis |
| Abstract: | 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. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 114316895 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Mereshchenko%2C+Andrey+S%2E%22">Mereshchenko, Andrey S.</searchLink><relatesTo>1</relatesTo><i> a.mereshchenko@spbu.ru</i><br /><searchLink fieldCode="AR" term="%22Olshin%2C+Pavel+K%2E%22">Olshin, Pavel K.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Myasnikova%2C+Olesya+S%2E%22">Myasnikova, Olesya S.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Panov%2C+Maxim+S%2E%22">Panov, Maxim S.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Kochemirovsky%2C+Vladimir+A%2E%22">Kochemirovsky, Vladimir A.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Skripkin%2C+Mikhail+Yu%2E%22">Skripkin, Mikhail Yu.</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Moroz%2C+Pavel+N%2E%22">Moroz, Pavel N.</searchLink><relatesTo>3,4</relatesTo><br /><searchLink fieldCode="AR" term="%22Zamkov%2C+Mikhail%22">Zamkov, Mikhail</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Tarnovsky%2C+Alexander+N%2E%22">Tarnovsky, Alexander N.</searchLink><relatesTo>3,4</relatesTo><i> atarnov@bgsu.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. Mar2016, Vol. 120 Issue 11, p1833-1844. 12p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Photochemistry+techniques%22">Photochemistry techniques</searchLink><br /><searchLink fieldCode="DE" term="%22Methanol%22">Methanol</searchLink><br /><searchLink fieldCode="DE" term="%22Acetonitrile+synthesis%22">Acetonitrile synthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+compounds+synthesis%22">Copper compounds synthesis</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/acs.jpca.5b12509 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 12 StartPage: 1833 Subjects: – SubjectFull: Photochemistry techniques Type: general – SubjectFull: Methanol Type: general – SubjectFull: Acetonitrile synthesis Type: general – SubjectFull: Ligands (Chemistry) Type: general – SubjectFull: Copper compounds synthesis Type: general Titles: – TitleFull: Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Mereshchenko, Andrey S. – PersonEntity: Name: NameFull: Olshin, Pavel K. – PersonEntity: Name: NameFull: Myasnikova, Olesya S. – PersonEntity: Name: NameFull: Panov, Maxim S. – PersonEntity: Name: NameFull: Kochemirovsky, Vladimir A. – PersonEntity: Name: NameFull: Skripkin, Mikhail Yu. – PersonEntity: Name: NameFull: Moroz, Pavel N. – PersonEntity: Name: NameFull: Zamkov, Mikhail – PersonEntity: Name: NameFull: Tarnovsky, Alexander N. IsPartOfRelationships: – BibEntity: Dates: – D: 24 M: 03 Text: Mar2016 Type: published Y: 2016 Identifiers: – Type: issn-print Value: 10895639 Numbering: – Type: volume Value: 120 – Type: issue Value: 11 Titles: – TitleFull: Journal of Physical Chemistry A Type: main |
| ResultId | 1 |
