Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?

Stockett, M. H.; Brøndsted Nielsen, S.

doi:10.1063/1.4919781

Title: Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?

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Abstract

Tris(bipyridine)ruthenium(II) (Ru(bipy){sub 3}{sup 2+}) is a prototypical transition metal coordination complex whose photophysical properties have attracted considerable attention. A much debated issue is whether the metal-to-ligand charge transfer (MLCT) transition that accounts for the complex’s beautiful red color is fully delocalized across all three bipyridine ligands or located on just one ligand. Here, we show based on gas-phase action spectroscopy that attachment of a single acetonitrile molecule does not change the absorption spectrum from that of the bare ions, which is indicative of a delocalized state. However, the gas-phase spectra of the bare and one solvent molecule complexes are significantly blueshifted relative to that obtained in bulk acetonitrile, which suggests that in solution the polarizability of many solvent molecules working together can localize the MLCT state. Our data clearly show that more than one solvent molecule is needed to break the symmetry of the MLCT excited state and reproduce its solution-phase characteristics.

Authors:

Stockett, M. H.; Brøndsted Nielsen, S. ^[1]

Department of Physics and Astronomy, Aarhus University, Aarhus (Denmark)

Publication Date:: Thu May 07 00:00:00 EDT 2015

OSTI Identifier:: 22415728

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 142; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ACETONITRILE; BIPYRIDINES; COLOR; EXCITED STATES; LIGANDS; MOLECULES; POLARIZABILITY; RUTHENIUM COMPLEXES; RUTHENIUM COMPOUNDS; SOLUTIONS; SOLVENTS; SYMMETRY

Citation Formats


                    Stockett, M. H., and Brøndsted Nielsen, S. Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?.  United States: N. p., 2015. 
        Web.  doi:10.1063/1.4919781.

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                    Stockett, M. H., & Brøndsted Nielsen, S. Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?.  United States.  https://doi.org/10.1063/1.4919781

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                    Stockett, M. H., and Brøndsted Nielsen, S. 2015.  
        "Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?".  United States.  https://doi.org/10.1063/1.4919781.

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@article{osti_22415728,

  title        = {Communication: Does a single CH{sub 3}CN molecule attached to Ru(bipy){sub 3}{sup 2+} affect its absorption spectrum?},

  author       = {Stockett, M. H. and Brøndsted Nielsen, S.},

  abstractNote = {Tris(bipyridine)ruthenium(II) (Ru(bipy){sub 3}{sup 2+}) is a prototypical transition metal coordination complex whose photophysical properties have attracted considerable attention. A much debated issue is whether the metal-to-ligand charge transfer (MLCT) transition that accounts for the complex’s beautiful red color is fully delocalized across all three bipyridine ligands or located on just one ligand. Here, we show based on gas-phase action spectroscopy that attachment of a single acetonitrile molecule does not change the absorption spectrum from that of the bare ions, which is indicative of a delocalized state. However, the gas-phase spectra of the bare and one solvent molecule complexes are significantly blueshifted relative to that obtained in bulk acetonitrile, which suggests that in solution the polarizability of many solvent molecules working together can localize the MLCT state. Our data clearly show that more than one solvent molecule is needed to break the symmetry of the MLCT excited state and reproduce its solution-phase characteristics.},

  doi          = {10.1063/1.4919781},

  url          = {https://www.osti.gov/biblio/22415728},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 17,

  volume       = 142,

  place        = {United States},

  year         = {Thu May 07 00:00:00 EDT 2015},

  month        = {Thu May 07 00:00:00 EDT 2015}

}

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