Position Dependent Effects of the Aza‐Substitution on the Electronic Properties and Crystal Structures Based on Hexaazaphenalene Isomers

We synthesized two hexaazaphenalene derivatives, 6AP-Pm (2,5-di(tert-butyl)-1,3,4,6,7,9b-hexaazaphenalene) and 6AP-Pz (2,5-di(tert-butyl)-1,3,4,6,8,9b-hexaazaphenalene) compared the electronic properties with pentaazaphenalene derivative 5AP (2,5-di(tert-butyl)-1,3,4,6,9b-pentaazaphenalene). clarified position-dependent effects of aza-substitution on states followed by optical electrochemical properties. In comparison to 5AP, had blue-shifted UV-vis absorption spectrum due lowered HOMO level slightly affected LUMO level. On other hand, showed red-shifted owing slightly-affected From theoretical investigations, it is suggested that one frontier molecular orbitals can be aza-substitution. Consequently, these opposite behaviors should induced in Furthermore, different favored packings crystalline state presumably because effect their dipole moments nitrogen atoms was varied. It demonstrated aromatic rings applicable not only for specifically modulating energy but also altering distributions crystal.