Bowl-shaped π-conjugated compounds offer the possibility to study curvature-dependent host–guest interactions and chemical reactivity in ideal model systems. For surface-adsorbed π bowls, however, only conformations with the bowl opening pointing away from the surface have been observed so far. Here we show for sumanene on Ag(111) that both bowl-up and bowl-down conformations can be stabilized. Analysis of the molecular layer as a function of coverage reveals an unprecedented structural phase transition involving a bowl inversion of one-third of the molecules. On the basis of scanning tunneling microscopy (STM) and complementary atomistic simulations, we develop a model that describes the observed phase transition in terms of a subtle interplay between inversion-dependent adsorption energies and intermolecular interactions. In addition, we explore the coexisting bowl-up and -down conformations with respect to host–guest binding of methane. STM reveals a clear energetic preference for methane binding to the concave face of sumanene.

Bowl Inversion of Surface-Adsorbed Sumanene / Jaafar, R.; Pignedoli, C. A.; Bussi, Giovanni; Aït Mansour, K.; Groening, O.; Amaya, T.; Hirao, T.; Fasel, R.; Ruffieux, P.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 136:39(2014), pp. 13666-13671. [10.1021/ja504126z]

Bowl Inversion of Surface-Adsorbed Sumanene

Bussi, Giovanni;
2014-01-01

Abstract

Bowl-shaped π-conjugated compounds offer the possibility to study curvature-dependent host–guest interactions and chemical reactivity in ideal model systems. For surface-adsorbed π bowls, however, only conformations with the bowl opening pointing away from the surface have been observed so far. Here we show for sumanene on Ag(111) that both bowl-up and bowl-down conformations can be stabilized. Analysis of the molecular layer as a function of coverage reveals an unprecedented structural phase transition involving a bowl inversion of one-third of the molecules. On the basis of scanning tunneling microscopy (STM) and complementary atomistic simulations, we develop a model that describes the observed phase transition in terms of a subtle interplay between inversion-dependent adsorption energies and intermolecular interactions. In addition, we explore the coexisting bowl-up and -down conformations with respect to host–guest binding of methane. STM reveals a clear energetic preference for methane binding to the concave face of sumanene.
2014
136
39
13666
13671
Jaafar, R.; Pignedoli, C. A.; Bussi, Giovanni; Aït Mansour, K.; Groening, O.; Amaya, T.; Hirao, T.; Fasel, R.; Ruffieux, P.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11767/11873
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