Lattice Opening Upon Bulk Reductive Covalent Functionalization of Black Phosphorus

This is the peer reviewed version of the following article: Wild, S., Fickert, M., Mitrovic, A., Lloret, V., Neiss, C., Vidal¿Moya, J. A., ... & Hirsch, A. (2019). Lattice opening upon bulk reductive covalent functionalization of black phosphorus. Angewandte Chemie International Edition, 58(17), 5763-5768, which has been published in final form at https://doi.org/10.1002/anie.201811181. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] 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.A.H. and G.A. acknowledge the European Research Council (ERC Advanced Grant 742145 B-PhosphoChem to A.H., and ERC Starting Grant 2D-PnictoChem 804110 to G.A.) for support. The research leading to these results was partially funded by the European Union Seventh Framework Programme under grant agreement No. 604391 Graphene Flagship. G.A. has received financial support through the Postdoctoral Junior Leader Fellowship Programme from "la Caixa" Banking Foundation (LCF/BQ/PI18/11630018). G.A. thanks the Deutsche Forschungsgemeinschaft (DFG; FLAG-ERA AB694/2-1), the Generalitat Valenciana (SEJI/2018/034 grant), and the FAU (Emerging Talents Initiative grant #WS16-17_Nat_04) for support. A.H. and A.G. thank the SFB 953 "Synthetic Carbon Allotropes" funded by the DFG for support and the Cluster of Excellence "Engineering of Advanced Materials". A.G. is grateful for funding from the Free State of Bavaria (Research Network "Solar Technologies go Hybrid"). A.M. thanks the Alexander von Humboldt (AvH) Foundation for a postdoctoral fellowship. This work was supported by the MINECO (Spain) through the Excellence Unit Maria de Maeztu (MDM-2015-0538) and the Project CTQ2017-86735-P.Wild, S.; Fickert, M.; Mitrovic, A.; Lloret, V.; Neiss, C.; Vidal Moya, JA.; Rivero-Crespo, MÁ.... (2019). Lattice Opening Upon Bulk Reductive Covalent Functionalization of Black Phosphorus. Angewandte Chemie International Edition. 58(17):5763-5768. https://doi.org/10.1002/anie.20181118157635768581