Structure and bonding in rhodium coordination compounds: a 103Rh solid-state NMR and relativistic DFT study.

This study demonstrates the application of 103Rh solid-state NMR (SSNMR) spectroscopy to inorganic and organometallic coordination compounds, in combination with relativistic density functional theory (DFT) calculations of 103Rh chemical shift tensors and their analysis with natural bond orbital (NBO) and natural localized molecular orbital (NLMO) protocols, to develop correlations between 103Rh chemical shift tensors, molecular structure, and Rh-ligand bonding. 103Rh is one of the least receptive NMR nuclides, and consequently, there are very few reports in the literature. We introduce robust 103Rh SSNMR protocols for stationary samples, which use the broadband adiabatic inversion-cross polarization (BRAIN-CP) pulse sequence and wideband uniform-rate smooth-truncation (WURST) pulses for excitation, refocusing, and polarization transfer, and demonstrate the acquisition of 103Rh SSNMR spectra of unprecedented signal-to-noise and uniformity. The 103Rh chemical shift tensors determined from these spectra are complemented by NBO/NLMO analyses of contributions of individual orbitals to the 103Rh magnetic shielding tensors to understand their relationship to structure and bonding. Finally, we discuss the potential for these experimental and theoretical protocols for investigating a wide range of materials containing the platinum group elements.

Broadband Cross-Polarization to Half-Integer Quadrupolar Nuclei: Wideline Static NMR Spectroscopy.

Cross-polarization (CP) is a technique commonly used for the signal enhancement of NMR spectra; however, applications to quadrupolar nuclei have heretofore been limited due to a number of problems, including poor spin-locking efficiency, inconvenient relaxation times, and reduced CP efficiencies over broad spectral bandwidths─this is unfortunate, since they constitute 73% of NMR-active nuclei in the periodic table. The Broadband Adiabatic Inversion CP (BRAIN-CP) pulse sequence has proven useful for the signal enhancement of wideline and ultra-wideline (i.e., 250 kHz to several MHz in breadth) powder patterns arising from stationary samples; however, a comprehensive investigation of its application to half-integer quadrupolar nuclei (HIQN) is currently lacking. Herein, we present theoretical and experimental considerations for applying BRAIN-CP to acquire central-transition (CT, +1/2 ↔ -1/2) powder patterns of HIQN. Consideration is given to parameters crucial to the success of the experiment, such as the Hartmann-Hahn (HH) matching conditions and the phase modulation of the contact pulse. Modifications to the BRAIN-CP sequence such as flip-back (FB) pulses and ramped contact pulses applied to the 1H spins are used for the reduction of experimental times and increased CP bandwidth capabilities, respectively. Spectra for a series of quadrupolar nuclei with broad CT powder patterns, including 35Cl (S = 3/2), 55Mn (S = 5/2), 59Co (S = 7/2), and 93Nb (S = 9/2), are acquired via direct excitation (CPMG and WCPMG) and indirect excitation (CP/CPMG and BRAIN-CP) methods. We demonstrate that proper implementation of the sequence can enable 1H-S broadband CP over a bandwidth of 1 MHz, which to the best of our knowledge is the largest CP bandwidth reported to date. Finally, we establish the basic principles necessary for simplified optimization and execution of the BRAIN-CP pulse sequence for a wide range of HIQNs.