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Dipole amplification: a principle for the self-assembly of asymmetric monomers on metal surfaces.

Fabrication of structures with nanometer-size dimensions is a major research theme, and scanning probe microscopes have played a pivotal role in the discovery, characterization and manipulation of such structures. Maneuvering of individual atoms, molecules or bonds—one at a time—by means of the STM tip has been used to create a variety of structures on solid surfaces. Potentially more useful, however, is the versatile and frequently explored approach which involves the spontaneous formation of an architecture by association of its molecular constituents as a result of noncovalent interactions—self-assembly. Inspired by solid-state and solution-based supramolecular chemistry, self-assembled surface nanostructures have been realized by exploiting noncovalent interactions between adsorbed molecules, thereby relying mainly on hydrogenbonding or metal–ligand interactions. However, the symmetry and electronic structure of the underlying substrate atomic lattice may also play a significant role, for example, leading to the formation of extended periodic structures associated with charge-density waves. Here, we report the discovery of self-assembled, localized nanostructures of styrene, a-methylstyrene (a-MS), and trans-methylstyrene (TMS) (Figure 1) on theAg(100) surface. There are no possibilities for hydrogen-bonding or metal–ligand-type interactions in these three cases.