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 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 non-covalently bound dimers on the surface. The reaction mechanism and driving forces behind non-covalent association are discussed in light of density functional theory calculations.
Cite
@article{arxiv.2012.00494,
title = {Non-Covalent Dimerization after Enediyne Cyclization on Au(111)},
author = {Dimas G. de Oteyza and Alejandro Pérez Paz and Yen-Chia Chen and Zahra Pedramrazi and Alexander Riss and Sebastian Wickenburg and Hsin-Zon Tsai and Felix R. Fischer and Michael F. Crommie and Angel Rubio},
journal= {arXiv preprint arXiv:2012.00494},
year = {2020}
}