Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl42- Complex.
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| Title: | Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl |
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| Authors: | Mereshchenko, Andrey S.1 a.mereshchenko@spbu.ru, Myasnikova, Olesya S.1, Panov, Maxim S.1, Kochemirovsky, Vladimir A.1, Skripkin, Mikhail Yu.1, Budkina, Darya S.2,3, Tarnovsky, Alexander N.2,3 atarnov@bgsu.edu |
| Source: | Journal of Physical Chemistry B. May2017, Vol. 121 Issue 17, p4562-4568. 7p. |
| Subjects: | Solvents, Chemical relaxation, Copper chlorides |
| Abstract: | Nonradiative relaxation dynamics of CuCl42- complexes photoexcited into the highest-energy ligand-field electronic state (2A1) is studied in acetonitrile, dichloromethane, and chloroform solvents, as well as in acetonitrile-water and in acetonitrile-deuterated water mixtures. Due to ultrafast internal conversion, this excited state directly converts to the electronic ground state in dichloromethane and chloroform. The nonradiative relaxation constant is similar in anhydrous acetonitrile. Addition of water to acetonitrile solutions efficiently quenches the excited ligand-field 2A1 state. The quenching is proposed to be due to the diffusion-controlled formation of an electronically excited pentacoordinated [CuCl4H2O]2- encounter complex or a short-lived exciplex of similar structure, in which the electronic excitation energy transfers into the O-H stretch of the coordinated H2O molecule. This is followed by the dissociation of the pentacoordinated species, resulting in the reformation of the ground-state CuCl42- and free H2O molecules. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry B 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: 123850014 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl<subscript>4</subscript><superscript>2-</superscript> Complex. – 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="%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</relatesTo><br /><searchLink fieldCode="AR" term="%22Budkina%2C+Darya+S%2E%22">Budkina, Darya S.</searchLink><relatesTo>2,3</relatesTo><br /><searchLink fieldCode="AR" term="%22Tarnovsky%2C+Alexander+N%2E%22">Tarnovsky, Alexander N.</searchLink><relatesTo>2,3</relatesTo><i> atarnov@bgsu.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. May2017, Vol. 121 Issue 17, p4562-4568. 7p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Solvents%22">Solvents</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+relaxation%22">Chemical relaxation</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+chlorides%22">Copper chlorides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Nonradiative relaxation dynamics of CuCl42- complexes photoexcited into the highest-energy ligand-field electronic state (2A1) is studied in acetonitrile, dichloromethane, and chloroform solvents, as well as in acetonitrile-water and in acetonitrile-deuterated water mixtures. Due to ultrafast internal conversion, this excited state directly converts to the electronic ground state in dichloromethane and chloroform. The nonradiative relaxation constant is similar in anhydrous acetonitrile. Addition of water to acetonitrile solutions efficiently quenches the excited ligand-field 2A1 state. The quenching is proposed to be due to the diffusion-controlled formation of an electronically excited pentacoordinated [CuCl4H2O]2- encounter complex or a short-lived exciplex of similar structure, in which the electronic excitation energy transfers into the O-H stretch of the coordinated H2O molecule. This is followed by the dissociation of the pentacoordinated species, resulting in the reformation of the ground-state CuCl42- and free H2O molecules. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry B 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.jpcb.7b02015 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 4562 Subjects: – SubjectFull: Solvents Type: general – SubjectFull: Chemical relaxation Type: general – SubjectFull: Copper chlorides Type: general Titles: – TitleFull: Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl42- Complex. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Mereshchenko, Andrey S. – 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: Budkina, Darya S. – PersonEntity: Name: NameFull: Tarnovsky, Alexander N. IsPartOfRelationships: – BibEntity: Dates: – D: 04 M: 05 Text: May2017 Type: published Y: 2017 Identifiers: – Type: issn-print Value: 15206106 Numbering: – Type: volume Value: 121 – Type: issue Value: 17 Titles: – TitleFull: Journal of Physical Chemistry B Type: main |
| ResultId | 1 |
