Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling.

Autor: Walz Mitra KL; Department of Chemistry, University of Washington, 4000 15th Ave NE, Seattle, WA, 98195, USA., Chang CH; Department of Materials Science and Engineering, University of Washington, Seattle, WA, 98195, USA., Hanrahan MP; US DOE Ames Laboratory and Department of Chemistry, Iowa State University, Ames, IA, 50011, USA., Yang J; Department of Chemistry, University of Washington, 4000 15th Ave NE, Seattle, WA, 98195, USA., Tofan D; Department of Chemistry, University of Washington, 4000 15th Ave NE, Seattle, WA, 98195, USA., Holden WM; Department of Physics, University of Washington, Seattle, WA, 98195, USA., Govind N; Pacific Northwest National Laboratory, Richland, WA, 99352, USA., Seidler GT; Department of Physics, University of Washington, Seattle, WA, 98195, USA., Rossini AJ; US DOE Ames Laboratory and Department of Chemistry, Iowa State University, Ames, IA, 50011, USA., Velian A; Department of Chemistry, University of Washington, 4000 15th Ave NE, Seattle, WA, 98195, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Apr 12; Vol. 60 (16), pp. 9127-9134. Date of Electronic Publication: 2021 Mar 09.
DOI: 10.1002/anie.202016033
Abstrakt: Surface functionalization of two-dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface-specific protocol for the surface functionalization of few-layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X-ray photoelectron, solid state 31 P NMR, and UV-vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15 N-labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.
(© 2020 Wiley-VCH GmbH.)
Databáze: MEDLINE
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