PHOSPHORENE AND BLACK PHOSPHORUS: THE 31P NMR VIEW

Black phosphorus and phosphorene are attracting a large interest in the last years because of their great potential in many application fields [1]. In spite of this, the use of 31P NMR spectroscopy for characterizing these materials has been very limited so far. By exploiting Magic Angle Spinning (MAS) NMR experiments we have characterized for the first time the 31P-31P homonuclear dipolar couplings and the 31P shielding interactions, responsible for the NMR properties of black phosphorus (bP) and of its few-layer exfoliated form (fl-bP). It has been possible to identify the network of 31P nuclei more strongly dipolarly coupled and quantify their effective coupling. Moreover, with the support of DFT calculations, the 31P chemical shif tensors have been fully determined, highlighting two kinds of magnetically nonequivalent 31P nuclei [2]. 31P MAS NMR experiments have been successfully applied to fl-bP derived materials both in suspension and in solid polymeric matrices, obtaining interesting information on the state, modifications and interactions of fl-bP with polymers and functionalizing agents, opening the way to a more extensive NMR application to phosphorene based innovative materials for improving their structural knowledge and control [3,4]. References [1] M. Peruzzini, R. Bini, M. Bolognesi et al. Eur. J. Inorg. Chem. 1476-1494 (2019). [2] F. Martini, S. Borsacchi, G. Barcaro, M. Caporali, M. Vanni, M. Serrano-Ruiz, M. Geppi, M. Peruzzini, L. Calucci J. Phys. Chem. Lett.,10, 5122-5127 (2019). [3] E. Passaglia, F. Cicogna, F. Costantino et al. Chem. Mater. 30, 2036-2048 (2018). [4] M. Bolognesi, S. Moschetto