Title

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

Publication Date

12-18-2020

Department

Ames Laboratory; Chemistry

Campus Units

Chemistry, Ames Laboratory

OSTI ID+

1774051

Report Number

IS-J 10451

DOI

10.1002/anie.202016033

Journal Title

Angewandte Chemie International Edition

Volume Number

60

Issue Number

16

First Page

9127

Last Page

9134

Abstract

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 31P 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, 15N‐labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

DOE Contract Number(s)

AC02-07CH11358; AC05-76RL1830

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

Share

COinS