On-surface synthesis – Ullmann coupling reactions on N-heterocyclic carbene functionalized gold nanoparticles

Abstract

Organic on-surface syntheses promise to be a useful method for direct integration of organic molecules onto 2-dimensional (2D) flat surfaces. In the past years, there has been an increasing understanding of the mechanistic details of reactions on surfaces, however, mostly under ultra-high vacuum on very defined surfaces. Herein, we expand the scope to gold nanoparticles (AuNps) in solution via an Ullmann reaction of aryl halides connected via N-heterocyclic carbenes (NHCs) to AuNps. Through design and syntheses of various organic precursors, we address the influence of the contact angle, reactivity of the halogen and the proximity of the entire coupling partner on on-surface reactivities, thus, establishing general parameters governing organic on-surface syntheses on AuNps in solution, in comparison with the reactivity on defined surfaces under ultra-high vacuum. The retention of such halogenated Nps even at higher reaction temperatures holds great promise in the fields of materials engineering, nanotechnology and molecular self-assembly, while expanding the toolbox of organic chemistry synthesis in accessing various covalent architectures.