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Article Dans Une Revue Solid State Nuclear Magnetic Resonance Année : 2019

Analysis of HMQC experiments applied to a spin-1/2 nucleus subject to very large CSA


The acquisition of solid-state NMR spectra of "heavy" spin I = 1/2 nuclei, such as 119Sn, 195Pt, 199Hg or 207Pb can often prove challenging due to the presence of large chemical shift anisotropy (CSA), which can cause significant broadening of spectral lines. However, previous publications have shown that well-resolved spectra can be obtained via inverse 1H detection using HMQC experiments in combination with fast magic angle spinning. In this work, the efficiencies of different 195Pt excitation schemes are analyzed using SIMPSON numerical simulations and experiments performed on cis- and transplatin samples. These schemes include: hard pulses (HP), selective long pulses (SLP) and rotor-synchronized DANTE trains of pulses. The results show that for spectra of species with very large CSA, HP is little efficient, but that both DANTE and SLP provide efficient excitation profiles over a wide range of CSA values. In particular, it is revealed that the SLP scheme is highly robust to offset, pulse amplitude and length, and is simple to set up. These factors make SLP ideally suited to widespread use by "non-experts" for carrying out analyses of materials containing "heavy" spin I = 1/2 nuclei that are subject to very large CSAs. Finally, the existence of an "intermediate" excitation regime, with an rf-field strength in between those of HP and SLP, which is effective for large CSA, is demonstrated. It must be noted that in some samples, multiple sites may exist with very different CSAs. This is the case for 195Pt species with either square-planar or octahedral structures, with large or small CSA, respectively. These two types of CSAs can only be excited simultaneously with DANTE trains, which scale up the effective rf-field. Another way to obtain all the information is to perform two different experiments: one with SLP and the second with HP to excite the sites with moderate/large and small/moderate CSAs, respectively. These two complementary experiments, recorded with two different spinning speeds, can also be used to discriminate the center-band resonances from the spinning sidebands.
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Dates et versions

hal-04302990 , version 1 (23-11-2023)



Piotr Paluch, Andrew G. M. Rankin, Julien Trebosc, Olivier Lafon, Jean-Paul Amoureux. Analysis of HMQC experiments applied to a spin-1/2 nucleus subject to very large CSA. Solid State Nuclear Magnetic Resonance, 2019, Solid State Nuclear Magnetic Resonance, 100, pp.11-25. ⟨10.1016/j.ssnmr.2019.03.001⟩. ⟨hal-04302990⟩
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