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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]
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Database: Engineering Source
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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]
ISSN:15206106
DOI:10.1021/acs.jpcb.5b00744