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Synchrotron X\u2010ray diffraction showed the persistence of two previously unreported peaks related to the A7 structure in the pressure range of the simple\u2010cubic phase. The Rietveld refinement of the data demonstrates the occurrence of a two\u2010step mechanism for the A7 to simple\u2010cubic phase transition, indicating the existence of an intermediate pseudo simple\u2010cubic structure. From a chemical point of view this study represents a deep insight on the mechanism of interlayer bond formation during the transformation from the layered A7 to the non\u2010layered simple\u2010cubic phase of phosphorus, opening new perspectives for the design, synthesis and stabilization of phosphorene\u2010based systems. As superconductivity is concerned, a new experimental evidence to explain the anomalous pressure behavior of T<jats:sub>c<\/jats:sub> in phosphorus below 30\u2005GPa is provided.<\/jats:p>","DOI":"10.1002\/anie.201708368","type":"journal-article","created":{"date-parts":[[2017,9,21]],"date-time":"2017-09-21T11:28:58Z","timestamp":1505993338000},"page":"14135-14140","source":"Crossref","is-referenced-by-count":54,"title":["Interlayer Bond Formation in Black Phosphorus at High Pressure"],"prefix":"10.1002","volume":"56","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4856-0125","authenticated-orcid":false,"given":"Demetrio","family":"Scelta","sequence":"first","affiliation":[{"name":"ICCOM-CNR Institute of Chemistry of OrganoMetallic Compounds, National Research Council of Italy  Via Madonna del Piano 10 I-50019 Sesto Fiorentino Firenze Italy"},{"name":"LENS, European Laboratory for Non-linear Spectroscopy  Via N. 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