Spectroscopic and computational examination of a homologous series of rhodium(I) pybox carbonyl complexes has revealed a correlation between the conformation of the flanking aryl-substituted oxazoline donors and the carbonyl stretching frequency. This relationship is also observed experimentally for octahedral rhodium(III) and ruthenium(II) variants and cannot be explained through the classical, Dewar-Chatt-Duncanson, interpretation of metal-carbonyl bonding. Instead, these findings are reconciled by local changes in the magnitude of the electric field that is projected along the metal-carbonyl vector: the internal Stark effect.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10092048PMC
http://dx.doi.org/10.1002/chem.202202283DOI Listing

Publication Analysis

Top Keywords

carbonyl stretching
8
internal stark
8
modulation metal
4
metal carbonyl
4
stretching frequencies
4
frequencies second
4
second coordination
4
coordination sphere
4
sphere internal
4
stark spectroscopic
4

Similar Publications

Heavy fuel oil (HFO) stranded on the coastline poses a potential threat to the health of marine fish after an oil spill. In this study, an oiled-gravel-column (OGC) system was established to investigate the toxic effects of stranded HFO on marine medaka Oryzias melastigma. HFO 380# (sulfur content 2.

View Article and Find Full Text PDF

Effects of Cosolvent and Nonsolvating Solvent on the Structural Dynamics of Organic Electrolytes in Sodium-Ion Batteries.

ACS Appl Mater Interfaces

December 2024

Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.

In sodium-ion batteries (SIBs), the performance of a single solvent often does not meet actual requirements and a cosolvent or nonsolvating solvent is needed. However, the effect of these electrolyte additives on the solvation structure and dynamics of Na in SIBs is yet to be fully understood. Herein, electrolyte structural dynamics are examined for NaPF in dimethyl carbonate (DMC) with 1,1,2,2-tetrafluoro-2,2,2-trifluoroethoxy ethane (HFE) as the nonsolvating solvent or propylene carbonate (PC) as the cosolvent using steady-state and time-resolved infrared (IR) spectroscopies.

View Article and Find Full Text PDF

Probing the anharmonicity of vibrational polaritons with double-quantum two-dimensional infrared spectroscopy.

Nanophotonics

June 2024

Schulich Faculty of Chemistry, Solid State Institute, and Helen Diller Quantum Center, Technion - Israel Institute of Technology, Haifa 3200003, Israel.

Strong coupling between the molecular vibrations and electromagnetic fields of light confined to an infrared cavity leads to the formation of vibro-polaritons - quasi-particles thought to provide the means to control the rates of chemical reactions inside a dark cavity. Despite the mechanisms indicating how vibrational coupling to the vacuum fields can affect the reaction rates are still not well understood, it has been recently demonstrated that the formation of the polariton states alters the ultrafast relaxation dynamics of the strongly coupled system. The relaxation dynamics in molecules, which is known to be important for the chemical reactivity, is directed by anharmonic couplings involving multiple intra- and inter-molecular vibrational degrees of freedom.

View Article and Find Full Text PDF

The intermediate phase produced by the complexation of metal ions and solvent molecules usually occurs in the crystallization process of perovskite single crystal or film. Effective monitoring of intermediate-phase evolution is beneficial to the control of crystal quality. However, it is difficult to realize.

View Article and Find Full Text PDF

KTiOPO (KTP) nanoparticles (NPs) are potential materials as biolabels for long-term imaging. Optimizing their properties can lead to higher imaging efficiency and lower cytotoxicity and side effects. In this study, these nanoparticles were synthesized using the co-precipitation method and capping agents of oxalic acid and glycine.

View Article and Find Full Text PDF

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!