X-ray absorption spectroscopy (XAS) is a powerful tool for examining changes of the electronic and molecular structure following light-induced excitation of a molecule. Specifically, this method can be applied to investigate the ground (GS, RuNO) and metastable states (MS1, RuON and MS2, Ruη(NO)) of the nitrosyl ligand (NO), which differ in their coordination mode to the metal. In this work, we report for the first time experimental and theoretical (DFT) Ru L,-edge XA spectra for the octahedral complex trans-[RuNOPyF](ClO) (1, Py = pyridine) in both ground and metastable states. The transition from GS to MS1 using 420 nm light excitation leads to a significant downshift of the 2p → LUMO(+1) peaks by about 0.5-0.8 eV, attributed to the destabilisation of 2p orbitals and stabilization of LUMO(+1). Subsequent irradiation of MS1 at 920 nm produces isomer MS2, for which even greater stabilization of LUMO occurs, though without a significant change in 2p energy. The change in 2p energy is attributed to a variation in the charge on the Ru atom after NO isomerization, while LUMO(+1) stabilization is related to changes in the Ru(NO) bond length and the composition of this orbital.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1016/j.saa.2024.125053 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Unlabelled: Proton exchange is a fundamental chemical event, and NMR provides the most direct readout of protonation events with site-specific resolution. Conventional approaches require manual titration of sample pH to collect a series of NMR spectra at different pH values. This requires extensive sample handling and often results in significant sample loss, leading to reduced signal or the need to prepare additional samples.
View Article and Find Full Text PDFLight-Induced Transformation from Covalent to Supramolecular Polymer Networks.
ACS Macro Lett
January 2025
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Stimuli-responsive polymers have demonstrated significant potential in the development of smart materials due to their capacity to undergo targeted property changes in response to external physical or chemical stimuli. However, the scales of response in most existing stimuli-responsive polymer systems are mainly focused on three levels: functional units, chain conformations, or polymer topologies. Herein, we have developed a covalent polymer network (CPN) capable of converting into a supramolecular polymer network (SPN) within bulk materials directly at the scale of polymer network types.
View Article and Find Full Text PDFLight-dependent Br-org production in terrestrial plants under acetaminophen stress and the bromination mechanisms mediated by photosystem.
J Environ Sci (China)
July 2025
School of Environmental Science and Engineering, Shandong Key Laboratory of Environmental Processes and Health, Shandong University, Qingdao 266237, China; Laboratory of Marine Ecological Environment in Universities of Shandong, Shandong University, Qingdao 266237, China; Qingdao Key Laboratory of Marine Pollutant Prevention, Shandong University, Qingdao 266237, China; Shandong Kenli Petrochemical Group Co., Ltd., Dongying 257500, China. Electronic address:
Due to the endocrine toxicity, neurotoxic, and reproductive toxicity to organisms, the sources and risks of brominated organic pollutants have attracted widespread attention. However, knowledge gaps remain in the bromination processes of emerging phenolic pollutants in plants, which may increase the potential health risk associated with food exposure. Our study discovered that light induced generation and accumulation of more toxic brominated organic compounds (Br-org) in lettuce leaves under the stress of acetaminophen (ACE) than that without light, as evidenced by an increase in C-Br bond intensity in FTIR analysis.
View Article and Find Full Text PDFRapid-Scan Fourier Transform Infrared Difference Spectroscopy with Two-Dimensional Correlation Analysis to Show the Build-Up of Light-Adapted States in Bacterial Photosynthetic Reaction Centers.
Appl Spectrosc
January 2025
Department of Materials Science and Engineering, University of Delaware, Newark, DE, USA.
Time-resolved, rapid-scan Fourier transform infrared (FT-IR) difference spectra have been recorded upon illumination on photosynthetic reaction centers (RCs) from under fixed hydration conditions (relative humidity = 76%). Two different illumination schemes were adopted. Whereas the use of a laser flash (duration: 7 ns) made it possible to follow the kinetics of recombination of the light-induced state PQ to the neutral state PQ, the use of a 20.
View Article and Find Full Text PDFClinical outcome and volumetric 3D analysis of biofluorescence imaging system guided surgery for Medication-Related Osteonecrosis of the Jaw(MRONJ).
BMC Oral Health
January 2025
Department of Oral and Maxillofacial Surgery, Section of Dentistry, Seoul National University Bundang Hospital, 82 Gumi-ro 173 beon-gil, Bundang-gu, Bundang‑gu, 13620, Seongnam, Republic of Korea.
Background: This study aims to evaluate the clinical outcome of biofluorescent imaging system (BIS) guided MRONJ surgery through analyzing 3D volumetric changes in CBCT data of bone structure.
Methods: BIS-guided surgery for MRONJ surgery was performed by grinding red-fluorescent area from remained residual bone detected by Qray-pen. CBCT data was collected preoperatively, postoperatively, and at last follow-up more than 3 months of each patient.
Want 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!