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Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl42- and IrBr62-.

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Title: Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl42- and IrBr62-.
Authors: Matveev, Sergey M.1, Mereshchenko, Andrey S.1, Panov, Maxim S.1, Tarnovsky, Alexander N.1 atarnov@bgsu.edu
Source: Journal of Physical Chemistry B. Apr2015, Vol. 119 Issue 14, p4857-4864. 8p.
Subjects: Near infrared spectroscopy, Excited state chemistry, Copper compounds, Femtosecond pulses, Metal complexes
Abstract: Ultrafast transient absorption spectroscopy is used to investigate the radiationless relaxation dynamics of CuCl42- and IrBr62- complexes directly promoted into their lowest-energy excited metal-centered states upon near-infrared femtosecond excitation at 2000 nm. Both the excited CuCl42-²E and IrBr62-²Ug'(T2g) states undergo internal conversion to the ground electronic states, yet with significantly different lifetimes (55 fs and 360 ps, respectively) despite the fact that the ²E and ²Ug'(T2g) states are separated by the same energy gap (~5000 cm-1) from the respective ground state. This difference likely arises from the predominance of the Jahn-Teller effect in a Cu2+ ion and the spin-orbit coupling effect in an Ir4+ ion. The approach documented in this work may be used for elucidating the role of low-energy metal-centered states in relaxation cascades of a number of coordination compounds, allowing for design of efficient light-triggered metal complexes. [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
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DbLabel: Engineering Source
An: 102123440
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PubType: Academic Journal
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  Data: Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl<subscript>4</subscript><superscript>2-</superscript> and IrBr<subscript>6</subscript><superscript>2-</superscript>.
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  Data: <searchLink fieldCode="AR" term="%22Matveev%2C+Sergey+M%2E%22">Matveev, Sergey M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mereshchenko%2C+Andrey+S%2E%22">Mereshchenko, Andrey 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="%22Tarnovsky%2C+Alexander+N%2E%22">Tarnovsky, Alexander N.</searchLink><relatesTo>1</relatesTo><i> atarnov@bgsu.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. Apr2015, Vol. 119 Issue 14, p4857-4864. 8p.
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  Data: <searchLink fieldCode="DE" term="%22Near+infrared+spectroscopy%22">Near infrared spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Excited+state+chemistry%22">Excited state chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+compounds%22">Copper compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Femtosecond+pulses%22">Femtosecond pulses</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink>
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  Label: Abstract
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  Data: Ultrafast transient absorption spectroscopy is used to investigate the radiationless relaxation dynamics of CuCl42- and IrBr62- complexes directly promoted into their lowest-energy excited metal-centered states upon near-infrared femtosecond excitation at 2000 nm. Both the excited CuCl42-²E and IrBr62-²Ug'(T2g) states undergo internal conversion to the ground electronic states, yet with significantly different lifetimes (55 fs and 360 ps, respectively) despite the fact that the ²E and ²Ug'(T2g) states are separated by the same energy gap (~5000 cm-1) from the respective ground state. This difference likely arises from the predominance of the Jahn-Teller effect in a Cu2+ ion and the spin-orbit coupling effect in an Ir4+ ion. The approach documented in this work may be used for elucidating the role of low-energy metal-centered states in relaxation cascades of a number of coordination compounds, allowing for design of efficient light-triggered metal complexes. [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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      – Type: doi
        Value: 10.1021/acs.jpcb.5b00744
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 8
        StartPage: 4857
    Subjects:
      – SubjectFull: Near infrared spectroscopy
        Type: general
      – SubjectFull: Excited state chemistry
        Type: general
      – SubjectFull: Copper compounds
        Type: general
      – SubjectFull: Femtosecond pulses
        Type: general
      – SubjectFull: Metal complexes
        Type: general
    Titles:
      – TitleFull: Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl42- and IrBr62-.
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            NameFull: Matveev, Sergey M.
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            NameFull: Mereshchenko, Andrey S.
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            NameFull: Panov, Maxim S.
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            NameFull: Tarnovsky, Alexander N.
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            – D: 09
              M: 04
              Text: Apr2015
              Type: published
              Y: 2015
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              Value: 119
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              Value: 14
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            – TitleFull: Journal of Physical Chemistry B
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