Tuning the Structure and Properties of N‐doped Positively Charged Polycyclic Aromatic Hydrocarbons

A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N‐doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic‐zero version of the continuous transformation of origin of current density (CTOCD‐DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N‐atoms in the inner rings was found to cause a planarity distortion in the studied N‐doped systems. The geometric changes and charged nature of the studied N‐doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties. Incorporation of N‐atoms into the inner rings of large polycyclic aromatic hydrocarbons (PAHs) results in significant planarity deviation and molecular dipole moment change. On the other hand, the induced current densities and aromatic character remain practically unchanged relative to the corresponding undoped PAH molecules.