The advancement of organic optoelectronics relies heavily on polycyclic aromatic compounds (PACs), which act as fundamental components in these devices. Unfortunately, their hydrocarbon counterparts, polycyclic aromatic hydrocarbons (PAHs), particularly acenes, often suffer from poor stability. Major decomposition pathways, such as photooxidation with 1 O 2 and oligomerization, are closely linked to the HOMO and LUMO energy levels of acenes. Therefore, finding ideal systems for organic optoelectronic applications with tunable energy levels of frontier molecular orbitals, alongside maintaining good stability and solubility is a highly challenging task.