Pyridinic Nitrogen Modification for Selective Acetylenic Homocoupling on Au(111)

• Published in: Journal of the American Chemical Society 2023-03, Vol.145 (8), p.4545-4552
• Main Authors: Li, Xuechao, Niu, Kaifeng, Duan, Sai, Tang, Yanning, Hao, Zhengming, Xu, Zhichao, Ge, Haitao, Rosen, Johanna, Björk, Jonas, Zhang, Haiming, Xu, Xin, Chi, Lifeng
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.2c11799

On-surface acetylenic homocoupling has been proposed to construct carbon nanostructures featuring sp hybridization. However, the efficiency of linear acetylenic coupling is far from satisfactory, often resulting in undesired enyne products or cyclotrimerization products due to the lack of strategies to enhance chemical selectivity. Herein, we inspect the acetylenic homocoupling reaction of polarized terminal alkynes (TAs) on Au(111) with bond-resolved scanning probe microscopy. The replacement of benzene with pyridine moieties significantly prohibits the cyclotrimerization pathway and facilitates the linear coupling to produce well-aligned N-doped graphdiyne nanowires. Combined with density functional theory calculations, we reveal that the pyridinic nitrogen modification substantially differentiates the coupling motifs at the initial C–C coupling stage (head-to-head vs head-to-tail), which is decisive for the preference of linear coupling over cyclotrimerization.