Solid State NMR Connectivity Studies in Dipolarly Coupled Inorganic Networks: Site Assignments in the Solid Electrolyte Material (CuI)8P12

Abstract

Abstract The local structure of the fast solid ion conductor Cu2P3I2 = (CuI)8P12 is investigated using one- and two-dimensional 31P and 65Cu magic-angle spinning NMR techniques. Peak assignments are proposed on the basis of anisotropic and isotropic spin-spin interactions recovered via radio frequency driven dipolar recoupling (RFDR) and total through bond correlation spectroscopy (TOBSY) methods. Especially the previously proposed R306 14 pulse symmetry (R-TOBSY), which exploits scalar spin-spin interactions for coherence transfer, offers outstanding spectral selectivity with respect to 1 J coupling. Using sufficiently short mixing times it is thus possible to correlate selectively those 31P spins that are directly bonded, thereby providing detailed insights into phosphorus-phosphorus connectivities in the network. The final assignment of the nine resolved 31P resonances to the twelve crystallographically distinct phosphorus sites suggests a significant relationship between 31P chemical shifts and the detailed pyramidal P(P1/3)3 bonding geometry.