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Terminal Alkyne Coupling on a Corrugated Noble Metal Surface: From Controlled Precursor Alignment to Selective Reactions
Author(s) -
Lin Tao,
Zhang Liding,
Björk Jonas,
Chen Zhi,
Ruben Mario,
Barth Johannes V.,
Klappenberger Florian
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701735
Subject(s) - coupling reaction , alkyne , pentamer , scanning tunneling microscope , dehydrogenation , covalent bond , noble metal , materials science , photochemistry , monomer , metal , chemistry , chemical physics , nanotechnology , catalysis , organic chemistry , biochemistry , polymer
Surface‐templated covalent coupling of organic precursors currently emerges as a promising route to the atom‐precise fabrication of low‐dimensional carbon materials. Here, we investigate the adsorption and the coupling reactions of 4,4 ′′ ‐diethynyl‐1,1 ′ :4 ′ ,1 ′′ ‐terphenyl on Au(110) under ultra‐high vacuum conditions by using scanning tunneling microscopy combined with density functional theory and kinetic Monte Carlo calculations. Temperature treatment induces both 1,2,4‐asymmetric cyclotrimerization and homocoupling, resulting in various reaction products, including a previously unreported, surface‐templated H‐shaped pentamer. Our analysis of the temperature‐dependent relative product abundances unravels that 1,2,4‐trimerization and homocoupling proceed via identical intermediate species with the final products depending on the competition of coupling to a third monomer versus dehydrogenation. Our study sheds light on the control of coupling reactions by corrugated surfaces and annealing protocols.