We investigate the polymorphism of complexes formed by the hydration of a functionalized azobenzene molecule by low-temperature scanning tunneling microscopy. Under conditions at which the water-less azobenzene molecules remain as monomers on Au(111), co-adsorption of water leads to water–azobenzene complexes. These complexes prefer to adopt linear arrangements of the azobenzene mediated by its functionalized end groups. Such structures may serve as model systems for investigating the influence of a solvent on a surface reaction.

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