Hourglass‐Shaped Dendrimers on Surfaces: A Comparison of Different Scanning‐Tunneling‐Microscopy Approaches

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Abstract
Large molecules adsorbed on surfaces can be analyzed by scanning tunneling microscopy (STM) under various environmental conditions: on a dry surface in air or vacuum, and at the solid‐liquid interface. However, can measurements under dissimilar conditions be compared, e. g., when sample A was studied at the solid‐liquid interface and sample B in a dry environment? Only rarely can the same substance be examined with more than one approach, since completely different set‐up and preparations are necessary. Furthermore, few substances are suitable for several methods of sample preparation and characterization. We have chosen a large, flexible, nonplanar molecule, namely an alkoxy‐substituted second‐generation dendritic compound with a chiral core unit, which is peculiar for its ‘hourglass' conformation. The assembly properties have been explored by STM both in solution‐cast self‐organized monolayers (SOMs) and multilayer films, as well as at the solid‐liquid interface. The complexity and limits of the three approaches applied to our hourglass‐shaped dendritic compound are discussed. Depending on the approach and environmental conditions, several quality levels of image resolution could be achieved; measurements carried out at low temperatures led to highest resolution on the aromatic parts of the molecule. A comparison of equally sized images obtained under these varying conditions reveals not only different packing arrangements, but also spots of unlike shape. Therefore, when the approach, preparation, and/or environmental conditions are not the same, STM measurements of different compounds have to be compared with greatest care.