Dehydrogenation Induced Formation of Chiral Core-Shell Arrays of Melamine on Ag(111)

The structural evolution of supramolecular phases of melamine on Ag(111) surface as a function of annealing temperature is investigated by employing low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS). It is found that partial deprotonation of the melamine molecules leads to formation of distinct types of ordered supramolecular arrangements. Apart from two previously reported phases (alpha and beta), a new phase comprising arrays of close-packed hexagonal core-shell-type clusters is identified for the first time. Based on high-resolution STM images as well as structural modeling, we show that the new phase presents a two-level hierarchical order and chirality is expressed at both levels. Using STS characterization, we further reveal that the chiral arrangement of the clusters confines surface electrons into a honeycomb pathway with handedness, which could give rise to novel interfacial electronic properties such as Dirac fermions as well as flat band.