Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

• Published in: Angewandte Chemie International Edition Vol. 58; no. 17; pp. 5763 - 5768
• Main Authors: Wild, Stefan, Fickert, Michael, Mitrovic, Aleksandra, Lloret, Vicent, Neiss, Christian, Vidal‐Moya, José Alejandro, Rivero‐Crespo, Miguel Ángel, Leyva‐Pérez, Antonio, Werbach, Katharina, Peterlik, Herwig, Grabau, Mathias, Wittkämper, Haiko, Papp, Christian, Steinrück, Hans‐Peter, Pichler, Thomas, Görling, Andreas, Hauke, Frank, Abellán, Gonzalo, Hirsch, Andreas
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 16.04.2019; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: 31P NMR spectroscopy; black phosphorus; Communication; Communications; Covalence; covalent functionalization; Halides; Intercalation compounds; Organic chemistry; Phosphorus; Raman spectroscopy; reductive route; reductive route; covalent functionalization; black phosphorus; Raman spectroscopy; 31P NMR
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201811181

The chemical bulk reductive covalent functionalization of thin‐layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes. The reductive covalent functionalization of thin‐layer black phosphorus (BP) proceeds via BP intercalation compounds. Following the reductive activation of BP, the resulting charged BP reacts with alkyl halides and undergoes covalent functionalization. The BP lattice shows unprecedented opening and a higher degree of functionalization than that obtained by neutral routes.