Excited states of tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)], can be deactivated by a wide range of ferrocene derivatives. The pathway by which deactivation takes place, either energy transfer (EnT) or electron transfer (ET), depends on several factors inherent to each specific donor-acceptor (D···A) system. In this work, we provide mechanistic insight into bimolecular quenching between [Ru(bpy)] and several ferrocene (Fc) derivatives in a variety of solvents. By introducing various functional groups onto the cyclopentadienyl ring of ferrocene, the chemical properties of the organometallic complexes were altered by tuning the oxidation potentials and charge of the iron complexes, and the manner in which the [Ru(bpy)] excited state is quenched by each ferrocene complex in solvents of various dielectric constants, including anhydrous acetonitrile (ACN), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and water (pH 10), was assessed. Through the use of transient absorption (TA) spectroscopy, the mechanism of [Ru(bpy)] quenching by each of five ferrocene derivatives (i.e., either EnT or ET) in the aforementioned solvents was evaluated. On the basis of these studies, electrostatic factors relating to the charge on the ferrocene moiety were found to influence the quenching pathway(s) for the [Ru(bpy)]···Fc systems under interrogation. When the ferrocene moiety is positively charged, the [Ru(bpy)] excited state is quenched by EnT to Fc, while when the ferrocene moiety is neutral or negatively charged, the [Ru(bpy)] excited state is quenched via reductive ET.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jpca.9b04427 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ab initio machine-learning unveils strong anharmonicity in non-Arrhenius self-diffusion of tungsten.
Nat Commun
January 2025
Institute for Materials Science, University of Stuttgart, D-70569, Stuttgart, Germany.
The knowledge of diffusion mechanisms in materials is crucial for predicting their high-temperature performance and stability, yet accurately capturing the underlying physics like thermal effects remains challenging. In particular, the origin of the experimentally observed non-Arrhenius diffusion behavior has remained elusive, largely due to the lack of effective computational tools. Here we propose an efficient ab initio framework to compute the Gibbs energy of the transition state in vacancy-mediated diffusion including the relevant thermal excitations at the density-functional-theory level.
View Article and Find Full Text PDFAggregation-induced emission and absorption enhancement of mixed-valent rhenium oxide quantum dots by triethylamine: Implications for food safety monitoring.
J Hazard Mater
December 2024
Department of Chemistry, National Sun Yat-sen University, No. 70 Lienhai Rd., Kaohsiung 80424, Taiwan; Center for Nanoscience & Nanotechnology, National Sun Yat-sen University, No. 70 Lienhai Rd., Kaohsiung 80424, Taiwan; School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, No.100, Shiquan 1st Rd., Kaohsiung 80708, Taiwan. Electronic address:
Food freshness monitoring and volatile amine detection are key to food safety. In this study, we demonstrated the applicability of mixed-valence rhenium oxide quantum dots (MV-ReOQDs), synthesized via the hydrothermal reaction of α-cyclodextrin and rhenium ion precursors, in triethylamine (TEA) sensing. Spectroscopic correlation techniques showed that the developed MV-ReOQDs possessed mixed-valent rhenium, α-cyclodextrin as capped ligand, partially carbonized surface, and amorphous phase structure.
View Article and Find Full Text PDFAnisotropic Plasmon Resonance in TiCT MXene Enables Site-Selective Plasmonic Catalysis.
ACS Nano
January 2025
Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, PR China.
The ever-growing interest in MXenes has been driven by their distinct electrical, thermal, mechanical, and optical properties. In this context, further revealing their physicochemical attributes remains the key frontier of MXene materials. Herein, we report the anisotropic localized surface plasmon resonance (LSPR) features in TiCT MXene as well as site-selective photocatalysis enabled by the photophysical anisotropy.
View Article and Find Full Text PDFActive Physics-Informed Deep Learning: Surrogate Modeling for Nonplanar Wavefront Excitation of Topological Nanophotonic Devices.
Nano Lett
January 2025
Institute of Experimental and Applied Physics, Kiel University, Leibnizstr. 11-19, Kiel 24098, Germany.
Topological plasmonics combines principles of topology and plasmonics to provide new methods for controlling light, analogous to topological edge states in photonics. However, designing such topological states remains challenging due to the complexity of the high-dimensional design space. We present a novel method that uses supervised, physics-informed deep learning and surrogate modeling to design topological devices for desired wavelengths.
View Article and Find Full Text PDFTracking the Geometric and Positional Isomerization of Lipid C═C Bonds in the Bacterial Stress Responses by Mass Spectrometry.
Anal Chem
January 2025
The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei 430072, China.
The position and configuration of the C═C bond have a significant impact on the spatial conformation of unsaturated lipids, which subsequently affects their biological functions. Double bond isomerization of lipids is an important mechanism of bacterial stress response, but its in-depth mechanistic study still lacks effective analytical tools. Here, we developed a visible-light-activated dual-pathway reaction system that enables simultaneous [2 + 2] cycloaddition and catalytic - isomerization of the C═C bond of unsaturated lipids via directly excited anthraquinone radicals.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!