Nanocorrals with different size, shape, and orientation are created on covalently modified highly oriented pyrolytic graphite surfaces using scanning probe nanolithography, i.e., nanoshaving. Alkylated diacetylene molecules undergo laterally confined supramolecular self-assembly within these corrals. When nanoshaving is performed in situ, at the liquid–solid interface, the orientation of the supramolecular lamellae structure is directionally influenced by the gradual graphite surface exposure. Careful choice of the nanoshaving direction with respect to the substrate symmetry axes promotes alignment of the supramolecular lamellae within the corral. Self-assembly occurring inside corrals of different size and shape reveals the importance of geometric and kinetic constraints controlled by the nanoshaving process. Finally, seed-mediated crystallization studies demonstrate confinement control over nucleation and growth principles.

A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry (CV) and chronoamperometry (CA) approaches are compared. The average diameter (45-130 nm) and surface density (20 to 125 corrals/µm 2) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and x-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated.

Nanocorrals created by scanning probe lithography on covalently modified graphite surfaces are used to induce a chiral bias in the enantiomorphic assembly of a prochiral molecule at the liquid/graphite interface. By controlling the orientation of the nanocorrals with respect to the underlying graphite surface, the nanocorral handedness can be freely chosen and thus a chiral bias in molecular self-assembly is created at an achiral surface solely by the scanning probe lithography process.

In situ nanocorrals on graphite yield oriented precursor self-assembly for controlled polymerization reactions.

The rotational degeneracy of the substrate is lifted when 2D supramolecular self-assembly is spatially confined via in situ STM nanoshaving.