The Molecular and Electronic Structure of Isolated Platinum Sites Enabled by Expedient Measurement of 195Pt Chemical Shift Anisotropy

Techniques that can characterize the molecular structures of dilute surface species are required to facilitate the rational synthesis and improvement of single-site and single-atom, such as the important class of Pt-based systems. In this context, 195Pt solid-state NMR spectroscopy could be an ideal tool for this task because 195Pt NMR spectra and sizeable chemical shift anisotropy (CSA) are highly sensitive probes of the local chemical environment and electronic structure. However, the broadening of 195Pt solid-state NMR spectra by CSA often results in low NMR sensitivity. Furthermore, characterization of Pt sites on surfaces is complicated by the typical low Pt loadings that are between 0.2 to 5 wt.%. Here, we introduce a set of solid-state NMR methods that exploit fast MAS and indirect detection of a sensitive spy nucleus (1H or 31P) to enable rapid acquisition of 195Pt MAS NMR spectra. We demonstrate that high-resolution wideline 195Pt MAS NMR spectra can be in minutes to a few hours for a series of molecular and single-site Pt species grafted on silica with Pt loading of only 3-5 wt.%. Low-power, long-duration, sideband-selective excitation and saturation pulses are incorporated into t1-noise eliminated (TONE) dipolar heteronuclear multiple quantum coherence (D-HMQC), perfect echo resonance echo saturation pulse double resonance (PE RESPDOR) or J-resolved pulse sequences. The complete 195Pt MAS NMR spectrum is then reconstructed by recording a series of 1D NMR spectra where the offset of the 195Pt pulses is varied. Analysis of the 195Pt MAS NMR spectra yields the 195Pt chemical shift tensor parameters. Analysis of the NMR signatures based on relativistic zeroth order approximation (ZORA) DFT calculations enables the rationalization of changes in the observed 195Pt CSA across the series of Pt compounds. Simple and predictive orbital models relate the measured spectral signatures to specific electronic environments and allows the identification of coordination environment by inspection of the CSA (isotropic chemical shift and measured spans). The methodology developed here paves the way for the detailed structural and electronic analysis of dilute platinum sites in single-atom and single-site heterogeneous catalysts.