Noncovalent Dimerization after Enediyne Cyclization on Au(111)

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• 作者：Dimas G. de Oteyza ; Alejandro Pérez Paz ; Yen-Chia Chen ; Zahra Pedramrazi ; Alexander Riss ; Sebastian Wickenburg ; Hsin-Zon Tsai ; Felix R. Fischer ; Michael F. Crommie ; Angel Rubio
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 31, 2016
• 年：2016
• 卷：138
• 期：34
• 页码：10963-10967
• 全文大小：376K
• 年卷期：0
• ISSN：1520-5126

文摘

We investigate the thermally induced cyclization of 1,2-bis(2-phenylethynyl)benzene on Au(111) using scanning tunneling microscopy and computer simulations. Cyclization of sterically hindered enediynes is known to proceed via two competing mechanisms in solution: a classic C¹–C⁶ (Bergman) or a C¹–C⁵ cyclization pathway. On Au(111), we find that the C¹–C⁵ cyclization is suppressed and that the C¹–C⁶ cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C¹–C⁶ product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.