On-surface synthesis of Au-C4 and Au-O4 alternately arranged organometallic coordination networks via selective aromatic C-H bond activation.

ABSTRACT

Selective activation of the C-H bond of aromatic hydrocarbons is significant in synthetic chemistry. However, achieving oriented C-H activation remains challenging due to the poor selectivity of aromatic C-H bonds. Herein, we successfully constructed alternately arranged Au-C4 and Au-O4 organometallic coordination networks through selective aromatic C-H bond activation on Au(111) substrate. The stepwise reaction process of the 5, 12-dibromopyrene 3,4,9, 10-tetracarboxylic dianhydride precursor is monitored by high-resolution scanning tunneling microscopy. Our results show that the gold atoms in C-Au-C organometallic chains play a crucial role in promoting the selective ortho C-H bonds activation and forming Au-C4 coordination structure, which is further demonstrated by a comparative experiment of PTCDA precursor on Au(111). Furthermore, our experiment of 2Br-PTCDA precursor on Cu(111) substrate confirms that copper atoms in C-Cu-C organometallic chains can also assist the formation of Cu-C4 coordination structure. Our results reveal the vital effect of organometallic coordination on selective C-H bond activation of reactants, which holds promising implications for controllable on-surface synthesis.