TY - JOUR
T1 - Noncovalent Dimerization after Enediyne Cyclization on Au(111)
AU - De Oteyza, Dimas G.
AU - Pérez Paz, Alejandro
AU - Chen, Yen Chia
AU - Pedramrazi, Zahra
AU - Riss, Alexander
AU - Wickenburg, Sebastian
AU - Tsai, Hsin Zon
AU - Fischer, Felix R.
AU - Crommie, Michael F.
AU - Rubio, Angel
N1 - Funding Information:
Research was supported by the U.S. Department of Energy Office of Basic Energy Sciences Nanomachine Program under Contract No. DE-AC02-05CH11231 (STM imaging), by the Office of Naval Research BRC Program (molecular synthesis), by the European Research Council Grants ERC-2010-AdG- 267374-DYNamo and ERC-2014-STG-635919-SURFINK (computational resources and surface analysis, respectively), by Spanish Grant No. FIS2013-46159-C3-1-P (simulated reaction landscape), and by Grupos Consolidados UPV/EHU del Gobierno Vasco No. IT-578-13 (simulated dimer binding energy). A.P.P. acknowledges postdoctoral fellowship support from Ayuda para la Especializacion de Personal Investigador del Vicerrectorado de Investigacion de la UPV/EHU-2013 and from the Spanish Juan de la Cierva-incorporacion program (IJCI-2014-20147). E. Goiri is acknowledged for help and discussion on the statistical analysis of interparticle distances.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/8/31
Y1 - 2016/8/31
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b05203
DO - 10.1021/jacs.6b05203
M3 - Article
AN - SCOPUS:84984801049
SN - 0002-7863
VL - 138
SP - 10963
EP - 10967
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 34
ER -