Application of self-assembly strategies to technologically relevant materials requires robust interactions between complex organic building blocks at surfaces. These studies lead us toward strategies to achieve crystalline, organic films with tailored chemical or physical functionality. Ionic bonding in supramolecular networks is a promising strategy to self-assemble nanostructures with atomic precision. However, sufficient stability in prototypical systems has not been achieved at metal surfaces, likely due to partial screening of the ionic interactions. Here, self-assembled ionic surface networks are formed by reaction of carboxylate species and an inexpensive ionic reagent, sodium chloride, and achieve a degree of thermal stability not previously demonstrated in self-assembled, non-covalent organic nanostructures at metal surfaces. Molecular-resolution imaging conducted at a sample temperature of 180 �C  illustrates atomic-level stability of the supramolecular architectures over many hours. In spite of the non-directionality of the electrostatic interactions, atomically-precise ordering into a robust phase is achieved for the first time through a cooperative effect of ionic interactions and metal�organic adsorption. Furthermore, complex carboxylate species that do not normally order at metal surfaces due to unfavorable adsorbate-substrate interactions can achieve self-organization via the utilized protocol. 

Self-assembly of robust supramolecular surface nanostructures by ionic bonding

246th National Meeting (2013)

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