Fivefold Symmetry and 2D Crystallization: Self-Assembly of the Buckybowl Pentaindenocorannulene on a Cu(100) Surface

Abstract

The modification of metal electrode surfaces with functional organic molecules is an important part of organic electronics. The interaction of the buckminsterfullerene fragment molecule pentaindenocorannulene with a Cu(100) surface is studied by scanning tunneling microscopy, dispersion-enabled density functional theory, and force field calculations. Experimental and theoretical methods suggest that two adjacent indeno groups become oriented parallel to the surface upon adsorption under mild distortion of the molecular frame. The binding mechanism between molecule and surface is dominated by strong electrostatic interaction owing to Pauli repulsion. Two-dimensional aggregation at room temperature leads to a single lattice structure in which all molecules are oriented unidirectionally. Their relative arrangement in the lattice suggests noncovalent intermolecular interaction through C-H⋅⋅⋅π bonding.

Keywords: 2D self-assembly; density functional theory; fullerenes; metal surfaces; scanning tunneling microscopy.