Pierre Kempgens

Determination of 1J(59Co–59Co) scalar coupling constants in the tetrahedral mixed-metal cluster HFeCo3(CO)10(PCyH2)(PPh2[CH2C(O)Ph]) using COSY-type NMR experiments

Two-dimensional ⁵⁹Co correlation spectroscopy (COSY) and double-quantum-filtered (DQF) COSY NMR experiments are reported for the tetrahedral mixed-metal cluster HFeCo₃(CO)₁₀(PCyH₂)(PPh₂[CH₂C(O)Ph]), which consists from the point of view of ⁵⁹Co NMR spectroscopy, of an AMX system of three-spin S=7/2. Both 2D NMR spectra prove the existence of a J scalar coupling constant between non-equivalent ⁵⁹Co nuclei. By contrast to what happens with the conventional 2D ⁵⁹Co COSY NMR spectrum, it was possible to simulate the 2D ⁵⁹Co DQF-COSY NMR spectrum by density matrix calculations in order to extract the values of the ¹J(⁵⁹Co-⁵⁹Co) coupling constants. The comparison between experimental and theoretical 2D NMR spectra gives spin-couplings constants of several hundreds Hertz for this cluster.

Powder-XRD and 14N magic angle-spinning solid-state NMR spectroscopy of some metal nitrides

Some metal nitrides (TiN, ZrN, InN, GaN, Ca3N2, Mg3N2, and Ge3N4) have been studied by powder X‐ray diffraction (XRD) and 14N magic angle‐spinning (MAS) solid‐state NMR spectroscopy. For Ca3N2, Mg3N2, and Ge3N4, no 14N NMR signal was observed. Low speed (νr = 2 kHz for TiN, ZrN, and GaN; νr = 1 kHz for InN) and ‘high speed’ (νr = 15 kHz for TiN; νr = 5 kHz for ZrN; νr = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder‐XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their 14N MAS solid‐state NMR spectrum matches perfectly well with the number of nitrogen‐containing phases identified by powder‐XRD. The 14N MAS solid‐state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Qccs arising from structural defects in the compounds studied. Copyright

Semi‐analytical description of the S = 9/2 quadrupole nutation NMR experiment: multinuclear application to 113In and 115In in indium phosphide

The density matrix of a spin S = 9/2 excited by a radiofrequency pulse is calculated. The interaction involved during the excitation of the spin system is first‐order quadrupolar. Consequently, the results are valid for any ratio of the quadrupolar coupling ωQ to the pulse amplitude ω1. The behavior of the central transition intensities versus the pulse length is discussed. The 115In and 113In nuclei in a powdered sample of indium phosphide (InP) are used to illustrate the results. It is found that the ratio of the quadrupolar coupling constants determined in this work is in excellent agreement with the ratio of the quadrupole moments of the two nuclei. Copyright

Investigation of the central line of 11B in hexagonal boron nitride by a one-dimensional single pulse nutation NMR experiment

Spin-3/2 central line intensities are calculated for any ratio of the quadrupolar coupling constant to the radiofrequency field for the one-pulse NMR experiment. The sequence is then used to obtain the quadrupolar coupling constant on a powder sample of hexagonal boron nitride. This technique is found to be particularly useful when the NMR spectrum is featureless.