title: Noncovalent Dimerization after Enediyne Cyclization on Au(111).
abstract: 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 C(1)-C(6) (Bergman) or a C(1)-C(5) cyclization pathway. On Au(111), we find that the C(1)-C(5) cyclization is suppressed and that the C(1)-C(6) cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C(1)-C(6) 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.
authors.affiliation: Donostia International Physics Center , E-20018 San Sebastián, Spain.|Ikerbasque, Basque Foundation for Science , E-48011 Bilbao, Spain.
authors.forename: Dimas G
authors.initials: DG
authors.lastname: de Oteyza
authors.affiliation: Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco, CFM CSIC-UPV/EHU-MPC , 20018 San Sebastián, Spain.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Pérez Paz
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.
authors.forename: Yen-Chia
authors.initials: YC
authors.lastname: Chen
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.
authors.forename: Zahra
authors.initials: Z
authors.lastname: Pedramrazi
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.
authors.forename: Alexander
authors.initials: A
authors.lastname: Riss
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Wickenburg
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.
authors.forename: Hsin-Zon
authors.initials: HZ
authors.lastname: Tsai
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Felix R
authors.initials: FR
authors.lastname: Fischer
authors.affiliation: Department of Physics, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Michael F
authors.initials: MF
authors.lastname: Crommie
authors.affiliation: Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco, CFM CSIC-UPV/EHU-MPC , 20018 San Sebastián, Spain.|Max Planck Institute for the Structure and Dynamics of Matter , Luruper Chaussee 149, 22761 Hamburg, Germany.|Center for Free-electron Laser Science (CFEL) , Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: Angel
authors.initials: A
authors.lastname: Rubio