Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo      Reveals Strong Dye-Dye Interactions

Christina Kjaer; Henriette Lissau; Nina Katharina Gravesen Salinas; Andreas Østergaard Madsen; Mark H. Stockett; Freja E. Storm; Thomas Holm Hansen; Jens Ulrik Andersen; Bo W. Laursen; Kurt V. Mikkelsen; Mogens Brøndsted Nielsen; Steen Brøndsted Nielsen

doi:10.1002/cphc.201800933

Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

Christina Kjaer, Henriette Lissau, Nina Katharina Gravesen Salinas, Andreas Østergaard Madsen, Mark H. Stockett, Freja E. Storm, Thomas Holm Hansen, Jens Ulrik Andersen, Bo W. Laursen, Kurt V. Mikkelsen, Mogens Brøndsted Nielsen, Steen Brøndsted Nielsen

Department of Chemistry

4 Citations (Scopus)

Abstract

Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH ₂ ) _n . In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.

Original language	English
Journal	ChemPhysChem
Volume	20
Issue number	4
Pages (from-to)	533-537
Number of pages	5
ISSN	1439-4235
DOIs	https://doi.org/10.1002/cphc.201800933
Publication status	Published - 18 Feb 2019

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Kjaer, C., Lissau, H., Gravesen Salinas, N. K., Østergaard Madsen, A., Stockett, M. H., Storm, F. E., Holm Hansen, T., Andersen, J. U., Laursen, B. W., Mikkelsen, K. V., Brøndsted Nielsen, M., & Brøndsted Nielsen, S. (2019). Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions. ChemPhysChem, 20(4), 533-537. https://doi.org/10.1002/cphc.201800933

Kjaer, C, Lissau, H, Gravesen Salinas, NK, Østergaard Madsen, A, Stockett, MH, Storm, FE, Holm Hansen, T, Andersen, JU, Laursen, BW , Mikkelsen, KV , Brøndsted Nielsen, M & Brøndsted Nielsen, S 2019, 'Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions', ChemPhysChem, vol. 20, no. 4, pp. 533-537. https://doi.org/10.1002/cphc.201800933

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title = "Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions",

abstract = " Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH 2 ) n . In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase F{\"o}rster Resonance Energy Transfer. ",

author = "Christina Kjaer and Henriette Lissau and Gravesen Salinas, {Nina Katharina} and Andreas {\O}stergaard Madsen and Stockett, {Mark H.} and Storm, {Freja E.} and Thomas Holm Hansen and Andersen, {Jens Ulrik} and Laursen, {Bo W.} and Mikkelsen, {Kurt V.} and Mogens Br{\o}ndsted Nielsen and Steen Br{\o}ndsted Nielsen",

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T1 - Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

AU - Kjaer, Christina

AU - Lissau, Henriette

AU - Gravesen Salinas, Nina Katharina

AU - Østergaard Madsen, Andreas

AU - Stockett, Mark H.

AU - Storm, Freja E.

AU - Holm Hansen, Thomas

AU - Andersen, Jens Ulrik

AU - Laursen, Bo W.

AU - Mikkelsen, Kurt V.

AU - Brøndsted Nielsen, Mogens

AU - Brøndsted Nielsen, Steen

PY - 2019/2/18

Y1 - 2019/2/18

N2 - Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH 2 ) n . In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.

AB - Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH 2 ) n . In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.

U2 - 10.1002/cphc.201800933

DO - 10.1002/cphc.201800933

M3 - Journal article

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SN - 1439-4235

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SP - 533

EP - 537

JO - ChemPhysChem

JF - ChemPhysChem

IS - 4

ER -

Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

Abstract

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