Simple Chemical Modification Using Perfluoroalkyl‐Substituted Stable Nitrile N‐Oxide on Bulk Surface via Catalyst‐Free Click Reaction

Abstract

Fluorinated surfaces show favorable physical properties for material applications. However, fluorination processes of bulk surfaces using conventional reagents require skilled techniques and special equipment. Herein, we demonstrate highly efficient surface modification using a new fluorination tool, perfluoroalkyl‐substituted stable nitrile N‐oxide. The nitrile N‐oxide is successfully synthesized in one‐pot by exploiting 1,1‐diphenylnitroethene as the precursor of nitrile N‐oxide. The nitrile N‐oxide exhibits not only high reactivity but also thermal stability, which enables the simple chemical modification of allyl group‐modified rigid surfaces without catalysts or byproducts. The surface is analysed by X‐ray photoelectron spectroscopy, time‐of‐flight secondary ion mass spectrometry, and contact angle measurements, providing clear evidence that the perfluoroalkyl groups are densely integrated on the bulk surface as a result of the efficient covalent bond formation.

Synthesis of Highly Stable and Reactive Nitrile N-Oxides and Their Application as Catalyst-Free Crosslinkers

“…Moreover, the complete disappearance of the FTIR absorption signal at around 2291 cm –1 confirmed the full conversion of nitrile N -oxides (Figure S16). Compared with the reported conditions, , the reactions with allyltrimethylsilane of these nitrile N -oxides needed a shorter time and a lower temperature, indicating that such a −CNO group had a higher reactivity. It is concluded that the methyl group as the sterically hindered group had little influence on the reactivity of the aromatic −CNO group.…”