TY - JOUR
T1 - Cryogenic fluorescence spectroscopy of ionic fluorones in gaseous and condensed phases: New light on their intrinsic photophysics
AU - Ashworth, Eleanor K.
AU - Langeland, Jeppe
AU - Stockett, Mark H.
AU - Lindkvist, Thomas Toft
AU - Kjær, Christina
AU - Bull, James N.
AU - Nielsen, Steen Brøndsted
N1 - The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.2c07231.
Funding information: Funding was provided by the Swedish Foundation for International Cooperation in Research and Higher Education (STINT, Grant No. PT2017-7328 to M.H.S. and J.N.B.) and an EPSRC New Investigator Award (EP/W018691 to J.N.B.). E.K.A. thanks the University of East Anglia for a doctoral studentship. S.B.N. acknowledges support from the NOVO Nordisk Foundation (Grant No. NNF20OC0064958) and Carlsbergfondet (Grant No. CF20-0097). Electronic structure calculations were carried out on the High Performance Computing Cluster supported by the Research and Specialist Computing Support service at the University of East Anglia.
PY - 2022/12/29
Y1 - 2022/12/29
N2 - Fluorescence spectroscopy of gas-phase ions generated through electrospray ionization is an emerging technique able to probe intrinsic molecular photophysics directly without perturbations from solvent interactions. While there is ample scope for the ongoing development of gas-phase fluorescence techniques, the recent expansion into low-temperature operating conditions accesses a wealth of data on intrinsic fluorophore photophysics, offering enhanced spectral resolution compared with room-temperature measurements, without matrix effects hindering the excited-state dynamics. This perspective reviews current progress on understanding the photophysics of anionic fluorone dyes, which exhibit an unusually large Stokes shift in the gas phase, and discusses how comparison of gas- and condensed-phase fluorescence spectra can fingerprint structural dynamics. The capacity for temperature-dependent measurements of both fluorescence emission and excitation spectra helps establish the foundation for the use of fluorone dyes as fluorescent tags in macromolecular structure determination. We suggest ideas for technique development.
AB - Fluorescence spectroscopy of gas-phase ions generated through electrospray ionization is an emerging technique able to probe intrinsic molecular photophysics directly without perturbations from solvent interactions. While there is ample scope for the ongoing development of gas-phase fluorescence techniques, the recent expansion into low-temperature operating conditions accesses a wealth of data on intrinsic fluorophore photophysics, offering enhanced spectral resolution compared with room-temperature measurements, without matrix effects hindering the excited-state dynamics. This perspective reviews current progress on understanding the photophysics of anionic fluorone dyes, which exhibit an unusually large Stokes shift in the gas phase, and discusses how comparison of gas- and condensed-phase fluorescence spectra can fingerprint structural dynamics. The capacity for temperature-dependent measurements of both fluorescence emission and excitation spectra helps establish the foundation for the use of fluorone dyes as fluorescent tags in macromolecular structure determination. We suggest ideas for technique development.
UR - http://www.scopus.com/inward/record.url?scp=85144471140&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.2c07231
DO - 10.1021/acs.jpca.2c07231
M3 - Article
VL - 126
SP - 9553
EP - 9563
JO - The Journal of Physical Chemistry A
JF - The Journal of Physical Chemistry A
SN - 1089-5639
IS - 51
ER -