Characterization of phosphorus clusters via multiple quantum solid state NMR

Nonclassical growth pathways have significant potential for development of materials with tunable functional complexity, however they remain mostly elusive to control due in significant part to the intrinsic difficulty of characterizing the highly dynamic structural evolution of prenucleation clusters. To firmly identify the structure of prenucleation clusters, solid-state NMR can be utilized to analyze various time points in nonclassical growth pathways via sample vitrification at < 100 K. We present ³¹P NMR spin counting studies of both powdered and vitrified phosphate containing samples, for which we have extracted the minimum number of dipolar coupled spins via the creation of multiple quantum coherence orders. Depending on sample and experimental conditions, intramolecular and intermolecular coherent spins can be probed. These quantitative measurements of ³¹P nuclei clustering in vitrified solutions provides a novel basis for the structural analysis of various nonclassical growth pathways.