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- El-Zohry, Ahmed, et al.
(author)
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Critical Role of Protons for Emission Quenching of Indoline Dyes in Solution and on Semiconductor Surfaces
- 2020
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In: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 124:39, s. 21346-21356
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Journal article (peer-reviewed)abstract
- By combining time-correlated single photon counting (TCSPC) measurements, density functional theory (DFT), and time-dependent DFT (TD-DFT) calculations, we herein investigate the role of protons, in solutions and on semiconductor surfaces, for the emission quenching of indoline dyes. We show that the rhodanine acceptor moieties, and in particular the carbonyl oxygens, undergo protonation, leading to nonradiative excited-state deactivation. The presence of the carboxylic acid anchoring group, close to the rhodanine moiety, further facilitates the emission quenching, by establishing stable H-bond complexes with carboxylic acid quenchers, with high association constants, in both ground and excited states. This complexation favors the proton transfer process, at a low quencher concentration, in two ways: bringing close to the rhodanine unit the quencher and assisting the proton release from the acid by a partial-concerted proton donation from the close-by carboxylic group to the deprotonated acid. Esterification of the carboxylic group, indeed, inhibits the ground-state complex formation with carboxylic acids and thus the quenching at a low quencher concentration. However, the rhodanine moiety in the ester form can still be the source of emission quenching through dynamic quenching mechanism with higher concentrations of protic solvents or carboxylic acids. Investigating this quenching process on mesoporous ZrO2, for solar cell applications, also reveals the sensitivity of the adsorbed excited rhodanine dyes toward adsorbed protons on surfaces. This has been confirmed by using an organic base to remove surface protons and utilizing cynao-acrylic dye as a reference dye. Our study highlights the impact of selecting such acceptor group in the structural design of organic dyes for solar cell applications and the overlooked role of protons to quench the excited state for such chemical structures.
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- El-Zohry, Ahmed M., et al.
(author)
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Highly Emissive Biological Bilirubin Molecules : Shedding New Light on the Phototherapy Scheme
- 2021
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In: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 125:32, s. 9213-9222
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Journal article (peer-reviewed)abstract
- Bilirubin (BR) is the main end-product of the hemoglobin catabolism. For decades, its photophysics has been mainly discussed in terms of ultrafast deactivation of the excited state in solution, where, indeed, BR shows a very low green emission quantum yield (EQY), 0.03%, resulting from an efficient nonradiative isomerization process. Herein, we present, for the first time, unique and exceptional photophysical properties of solid-state BR, which amend by changing the type of crystal, from a closely packed alpha crystal to an amorphous loosely packed beta crystal. BR alpha crystals show a very bright red emission with an EQY of ca. 24%, whereas beta crystals present, in addition, a low green EQY of ca. 0.5%. By combining density functional theory (DFT) calculations and time-resolved emission spectroscopy, we trace back this dual emission to the presence of two types of BR molecules in the crystal: a stiff monomer, M1, distorted by particularly strong internal H-bonds and a floppy monomer, M2, having a structure close to that of BR in solution. We assign the red strong emission of BR crystals to M1 present in both the alpha and beta crystals, while the low green emission, only present in the amorphous (beta) crystal, is interpreted as M2 emission. Efficient energy-transfer processes from M2 to M1 in the closely packed a crystal are invoked to explain the absence of the green component in its emission spectrum. Interestingly, these unique photophysical properties of BR remain in polar solvents such as water. Based on these unprecedented findings, we propose a new model for the phototherapy scheme of BR inside the human body and highlight the usefulness of BR as a strong biological fluorescent probe.
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- Eriksson K., Susanna, et al.
(author)
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Geometrical and energetical structural changes in organic dyes for dye-sensitized solar cells probed using photoelectron spectroscopy and DFT
- 2016
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 18:1, s. 252-260
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Journal article (peer-reviewed)abstract
- The effects of alkoxy chain length in triarylamine based donor acceptor organic dyes are investigated with respect to the electronic and molecular surface structures on the performance of solar cells and the electron lifetime. The dyes were investigated when adsorbed on TiO2 in a configuration that can be used for dye sensitized solar cells (DSCs). Specifically, the two dyes D35 and D45 were compared using photoelectron spectroscopy (PES) and density functional theory (DFT) calculations. The differences in solar cell characteristics when longer alkoxy chains are introduced in the dye donor unit are attributed to geometrical changes in dye packing while only minor differences were observed in the electronic structure. A higher dye load was observed for D45 on TiO2. However, D35 based solar cells result in higher photocurrent although the dye load is lower. This is explained by different geometrical structures of the dyes on the surface.
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