Photophysics of Isolated Rose Bengal Anions

Mark H. Stockett, Christina Kjaer, Steven Daly, Evan J. Bieske, Jan R. R. Verlet, Steen Brøndsted Nielsen, James Bull

Research output: Contribution to journalArticle

Abstract

Dye molecules based on the xanthene moiety are widely used as fluorescent probes in bioimaging and technological applications due to their large absorption cross-section for visible light and high fluorescence quantum yield. These applications require a clear understanding of the dye’s inherent photophysics and the effect of a condensed-phase environment. Here, the gas-phase photophysics of the rose bengal doubly deprotonated dianion [RB – 2H]2–, deprotonated monoanion [RB – H]−, and doubly deprotonated radical anion [RB – 2H]•– is investigated using photodetachment, photoelectron, and dispersed fluorescence action spectroscopies, and tandem ion mobility spectrometry (IMS) coupled with laser excitation. For [RB – 2H]2–, photodetachment action spectroscopy reveals a clear band in the visible (450–580 nm) with vibronic structure. Electron affinity and repulsive Coulomb barrier (RCB) properties of the dianion are characterized using frequency-resolved photoelectron spectroscopy, revealing a decreased RCB compared with that of fluorescein dianions due to electron delocalization over halogen atoms. Monoanions [RB – H]− and [RB – 2H]•– differ in nominal mass by 1 Da but are difficult to study individually using action spectroscopies that isolate target ions using low-resolution mass spectrometry. This work shows that the two monoanions are readily distinguished and probed using the IMS-photo-IMS and photo-IMS-photo-IMS strategies, providing distinct but overlapping photodissociation action spectra in the visible spectral range. Gas-phase fluorescence was not detected from photoexcited [RB – 2H]2– due to rapid electron ejection. However, both [RB – H]− and [RB – 2H]•– show a weak fluorescence signal. The [RB – H]− action spectra show a large Stokes shift of ∼1700 cm–1, while the [RB – 2H]•– action spectra show no appreciable Stokes shift. This difference is explained by considering geometries of the ground and fluorescing states.
Original languageEnglish
Pages (from-to)8429–8438
Number of pages10
JournalThe Journal of Physical Chemistry A
Volume124
Issue number41
Early online date23 Sep 2020
DOIs
Publication statusPublished - 15 Oct 2020

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