Rapid Acquisition of 103 Rh Solid-State NMR Spectra by 31 P Detection and Sideband Selective Methods
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide 103 Rh solid-state nuclear magnetic resonance (SSNMR) spectroscopy is potentially a powerful method for investigating the molecular and electronic structure of rhodium compounds. However, 103 Rh is a difficult nucleus to study by NMR spectroscopy because of its small gyromagnetic ratio, broad chemical shift range, and long spin–lattice relaxation times ( T 1 ). While there are many prior reports demonstrating acquisition of 103 Rh solution NMR spectra, there are few examples of 103 Rh SSNMR spectra in the literature. Here, we utilize the large 31 P- 103 Rh scalar couplings ( J -couplings) to efficiently acquire 31 P-detected high-resolution 103 Rh SSNMR spectra. 31 P{ 103 Rh} J -resolved NMR experiments were used to measure 31 P- 103 Rh J -couplings. Sideband selective SSNMR techniques originally developed for wide-line 195 Pt SSNMR experiments were then used to rapidly acquire 103 Rh SSNMR spectra. Notably, we were able to acquire MAS 103 Rh SSNMR spectra in experiment times on the order of 30 min to a few hours and from only a few mg of materials. The sideband selective experiments offer significant time savings as compared to existing direct detection methods, which require days of acquisition to obtain a directly detected MAS spectrum, or yield low-resolution static powder patterns. Numerical fits of the SSNMR spectra provide 103 Rh chemical shift tensor parameters, with the experimental spectra agreeing well with the DFT-calculated spectra.
DOI: 10.1021/jacs.5c00784
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4409493244