Rationalization of solid-state NMR multi-pulse decoupling strategies : coupling of spin I = ½ and half-integer quadrupolar nuclei

This work benefited from a grant from Agence Nationale de la Recherche (ANR MOSAIC 13-BS08-0018-01).In this paper we undertake a study of the decoupling efficiency of the Multiple-Pulse (MP) scheme, and a rationalization of its parameterization and of the choice of instrumental set up. This decoupling scheme is known to remove the broadening of spin-1/2 spectra I, produced by the heteronuclear scalar interaction with a half-integer quadrupolar nucleus S, without reintroducing heteronuclear dipolar interaction. The resulting resolution enhancement depends on the set-up of the length of the series of pulses and delays of the MP, and some intrinsic material and instrumental parameters. Firstly through a numerical approach, this study investigates the influence of the main intrinsic material parameters (heteronuclear dipolar and J coupling, quadrupolar interaction, spin nature) and instrumental parameters (spinning rate, pulse field strength) on efficiency and resolution enhancement of the scalar decoupling scheme. A guideline is then proposed to obtain quickly and easily the best resolution enhancement via the rationalization of the instrumental and parameter set up. It is then illustrated and tested through experimental data, probing the efficiency of MP-decoupling set up using this guideline. Various spin systems were tested (31P-51V in VOPO4, 31P-93Nb in NbOPO4, 119Sn-17O in Y2Sn2O7), combined with simulations results.PostprintPostprintPeer reviewe

Broadband excitation in solid-state NMR of paramagnetic samples using Delays Alternating with Nutation for Tailored Excitation ('Para-DANTE')

This Letter shows that interleaved sequences of short pulses in the manner of 'Delays Alternating with Nutation for Tailored Excitation' (DANTE) with N = 1,2,3 . . . equidistant pulses per rotor period extending over K rotor periods can be used to excite, invert or refocus a large number of spinning sidebands of spin-1/2 nuclei in paramagnetic samples where hyperfine couplings lead to very broad spectra that extend over more than 1 MHz. The breadth of the response is maintained for rf-field amplitudes as low as 30 kHz since it results from cumulative effects of individual pulses with very short durations

Study of Xenon Mobility in the Two Forms of MIL-53(Al) Using Solid-State NMR Spectroscopy

The Al-based metal–organic framework (MOF) MIL-53­(Al) exhibits a structural transition between a large-pore (<i>lp</i>) form and a narrow-pore (<i>np</i>) one. Such change is induced by temperature, external pressure, or the adsorption of guest molecules. ¹²⁹Xe solid-state NMR experiments under static and magic-angle spinning (MAS) conditions have been used to study the <i>lp</i>–<i>np</i> transition in MIL-53­(Al) initially loaded with xenon gas under a pressure of 5 × 10⁴ Pa (at room temperature). The conversion of the <i>lp</i> form into the <i>np</i> one when the temperature decreases from 327 to 237 K and the reopening of the pores below 230 K are then observed. Furthermore, ¹H → ¹²⁹Xe cross-polarization under MAS (CPMAS) experiments demonstrate the possibility to observe the <i>np</i> phase at <i>T</i> ≤ 230 K, while the <i>lp</i> one is unseen because the xenon residence time is too short for successful cross-polarization transfer. Moreover, even for the <i>np</i> phase at 199 K, the xenon atoms still exhibit significant motion on time scale faster than a few milliseconds. We prove the exchange of Xe atoms between the <i>lp</i> and <i>np</i> forms at room temperature with the two-dimensional (2D) ¹²⁹Xe EXchange SpectroscopY (EXSY) NMR method. Using ¹²⁹Xe selective inversion recovery (SIR) experiments, the rate for this exchange has been measured at 43 ± 6 s^–1

Méthodes d'analyse structurale par RMN haute résolution des noyaux quadripolaires et mesures des couplages à travers les liaisons et l'espace

Nous présentons ici les dernières techniques de RMN du solide de haute résolution sur les noyaux quadripolaires telles que le MQMAS, le STMAS, l'I-STMAS et quelques unes de leurs variantes. Nous insistons sur les limitations expérimentales de chacune. Dans un deuxième temps, nous décrivons le FS-J-RES qui pennet de mesurer précisément et sélectivement le couplage Jhétéronuc1éaire entre deux noyaux dont l'un peut être quadripolaire. Nous analysons en détail l'influence du pulse long sélectif fréquentiellement, notamment en présence de CSA sur le spin non observé. Cela nous permet d'introduire une formule analytique simple qui rend compte de la plupart des paramètres expérimentaux. Enfin, nous étendons la technique de mesure sélective de couplage dipolaire FS-REDOR au systèmes comportants un noyau quadripolaire. Nous analysons l'effet des pulses, en particulier en présence de CSA. Des résultats expérimentaux sont présentés sur l'histidine, la glycine et l'AIPO4 VPI5.LILLE1-BU (590092102) / SudocSudocFranceF

A comparison of through-space population transfers from half-integer spin quadrupolar nuclei to ¹H using MQ-HETCOR and MQ-SPAM-HETCOR under fast MAS.

International audienceIn this article, we compare the various schemes of magnetization transfer from half-integer quadrupolar spins to 1H nuclei and we establish an efficient protocol to perform these transfers under MQMAS high-resolution with the MQ-HETCOR and MQ-SPAM-HETCOR experiments under fast MAS. The MQMAS efficiencies are analyzed with SIMPSON simulations, and the CPMAS and RINEPT magnetization transfers are compared at 62.5 kHz MAS using {23Na}-1H and {27Al}-1H MQ-HETCOR and MQ-SPAM-HETCOR experiments performed on NaH2PO4, Na2HPO4, Na citrate dihydrate and ipa-AlPO-14 powder samples. We discuss the pros and cons of these approaches, aiming to record 2D spectra of the best possible quality under fast MAS. We also incorporate some experimental approaches to reduce the total experiment time of such long 2D experiments

Investigating the overall lattice structure and cation dynamics of post-synthetically treated MAPbI3 using a combination of X-ray diffraction and solid-state NMR

International audienc

Accelerating the acquisition of high-resolution quadrupolar MQ/ST-HETCOR 2D spectra under fast MAS via ¹H detection and through-space population transfers.

International audienceRecently, we established an experimental setup protocol to perform the population transfer from half-integer quadrupolar spin to 1H nuclei under fast MAS in the context of MQ-HETCOR experiments. In this article, we further develop the high-resolution 2D HETCOR methods by ST-based approaches, making use of the sensitivity advantage of STMAS over its MQMAS counterpart. In a similar manner to the previous work, which utilized CP and RINEPT for the population transfer, we also demonstrate the experimental setup protocol for PRESTO. Using {23Na}-1H and {27Al}-1H spin systems of powder samples, we compare a series of MQ/ST-HETCOR 2D spectra to discuss the pros and cons of the distinct MQ/ST-based approaches for spin 3/2 and 5/2 nuclei, respectively. We also incorporate two experimental tricks to reduce the experimental time of such long 2D experiments, the Optimized Rotor-Synchronization (ORS) and the Non-Uniform Sampling (NUS), in the context of high-resolution spectra of half-integer quadrupolar spin nuclei

Investigating the effects of post-synthetic treatments of MAPbI3 on its lattice structure and cation dynamics using X-ray diffraction and solid-state NMR

International audienc

Investigating the overall lattice structure and cation dynamics of post-synthetically treated MAPbI3 using a combination of X-ray diffraction and solid-state NMR

International audienc

Investigating the Effects of Post-Synthetically Treated MAPbI3 Using solid-state NMR and Synchrotron X-ray Diffraction

International audienc