Zigzag edges of graphene nanoribbons, which are predicted to host spin-polarized electronic states, hold great promise for future spintronic device applications. The ability to precisely engineer the zigzag edge state is of crucial importance for realizing its full potential functionalities in nanotechnology. By combining scanning tunneling microscopy and atomic force microscopy, we demonstrate the zigzag edge states have energy splitting upon fusing manganese the phthalocyanine molecule with the short armchair graphene nanoribbon termini. Moreover, the edge state splitting can be reversibly switched by adsorption and desorption of a hydrogen atom on the magnetic core of manganese phthalocyanine. These observations can be explained by tuning the zigzag edge local doping through the charge transfer process, which provides a new route to functionalize graphene-based molecular devices.

Triangulene and its homologues are of considerable interest for molecular spintronics due to their high-spin ground states as well as the potential for constructing high spin frameworks. Realizing triangulene-based high-spin system on surface is challenging but of particular importance for understanding π-electron magnetism. Here, we report two approaches to generate triangulene trimers on Au(111) by using surface-assisted dehydration and alkyne trimerization, respectively. We find that the developed dehydration reaction shows much higher chemoselectivity thus resulting in significant promotion of product yield compared to that using alkyne trimerization approach, through cutting the side reaction path. Combined with spin-polarized density functional theory calculations, scanning tunneling spectroscopy measurements identify the septuple (S = 3) high-spin ground state and quantify the collective ferromagnetic interaction among three triangulene units. Our results demonstrate the approaches to fabricate high-quality triangulene-based high spin systems and understand their magnetic interactions, which are essential for realizing carbon-based spintronic devices.

Coronoids as polycyclic aromatic macrocycles enclosing a cavity have attracted a lot of attention due to their distinctive molecular and electronic structures. They can be also regarded as nanoporous graphene molecules whose electronic properties are critically dependent on the size and topology of their outer and inner peripheries. However, because of their synthetic challenges, the extended hexagonal coronoids with zigzag outer edges have not been reported yet. Here, we report the on-surface synthesis of C144 hexagonal coronoid with outer zigzag edges on a designed precursor undergoing hierarchical Ullmann coupling and cyclodehydrogenation on the Au(111) surface. The molecular structure is unambiguously characterized by bond-resolved noncontact atomic force microscopy imaging. The electronic properties are further investigated by scanning tunneling spectroscopy measurements, in combination with the density functional theory calculations. Moreover, the values of the harmonic oscillator model of aromaticity are derived from calculations that suggest that the molecular structure is ideally represented by Clar's model. Our results provide approaches toward realizing a hexagonal coronoid with zigzag edges, potentially inspiring fabrication of hexagonal zigzag coronoids with multiple radical characters in the future.

Hydrogen-bonded molecules and their dynamics are significantly important in chemistry and biology due to their widespread functionality. Besides their natural abundance and diversity, applications of molecules with dynamic conformations in artificial networks allow information storage and molecular motor design on the nanometer scale. Here, we report hydrogen-bonded molecular networks with tunable helical conformation on metal surfaces. The dynamics of helical conformation in two-dimensional hydrogenbond networks are triggered and resolved by scanning probe microscopy at the single-molecule level. In combination with theoretical calculations, the surfacespecific hydrogen bonds are identified as the origin of the dynamic helical conformation. Our results provide a distinctive access to molecular architecture with tunable helical conformation driven by hydrogenbond interaction on surfaces.