Theoretical Modeling of the Self‐Assembly of Low‐Dimensional Superstructures With Exposed Nitrogen Coordination Centers

Construction of low-dimensional nitrogen-based nanostructures through self-assembly represents a promising strategy that can be effectively guided by theoretical methods. In this work, Monte Carlo simulations were employed to investigate the on-surface self-assembly of tricoordinate metal atoms and cyanofunctionalized pyridazine- and terpyridine-derived ligands bearing internal electron-donor nitrogen centers. The preferential coordination of metal atoms by terminal nitrile groups of these tectons was exploited to direct the self-assembly while maintaining the pyridine centers available for interactions with guest species. A series of positional isomers differing in cyanogroup placement was investigated to explore the range of planar structures formed by these tectons. The simulations demonstrated that appropriate cyanogroup placement within the molecule enables control over the position and exposure of nitrogen centers in self-assembled architectures, including networks, ladders, and chains with diverse geometries. The observed molecule-structure relationships may facilitate the rational design and optimization of functional nanostructures for applications in catalysis, sensing, separations, and related fields.