A DFT study on dihydropyrazine annulated linear polyacenes: aromaticity, stability and HOMO–LUMO energy modulation

Abstract

Linear polyacenes (LPAs) beyond pentacene are highly unstable and their application potential in the optoelectronics field is very limited. On the basis of theoretical studies at the M06L/6-311++G(d,p) level of DFT, we show that annulating dihydropyrazine units to LPA cores can yield large LPA mimics. This strategy enhances the aromaticity of the LPA core and also provides a way to modulate the HOMO–LUMO energy gap by choosing an appropriate LPA core and extending dihydropyrazine annulation. The study is conducted for LPA mimics containing up to six dihydropyrazine units annulated to benzene (pB₁–pB₆), naphthalene (pN₁–pN₆), anthracene (pA₁–pA₆) and tetracene (pT₁–pT₆) cores. The longest of them pT₆ contains 34 linearly connected six-membered rings. The dehydrogenation energy (E_dh) of the N-heterocycles of the LPA mimics showed endothermic character and indicated their higher stability than dehydrogenated N-heteroacenes. The total E_dh (ΣE_dh) is proportional to the increase in the number of heterocycles and the increase in the size of the LPA core. The aromaticity of individual rings of all the LPA mimics is assessed on the basis of the harmonic oscillator model of aromaticity (HOMA) and nucleus independent chemical shift (NICS) parameters. Both parameters showed strong linear correlation with ΣE_dh, confirming the geometric, magnetic and energetic criteria of aromaticity. The electronic features of the LPA mimics assessed by analysing molecular electrostatic potential topography and molecular orbitals have shown that the LPA cores retain the reactivity of the parent LPA. Furthermore, significant mixing of the N-lone pairs of the heterocycle with carbon π-orbitals improves aromaticity and decreases the HOMO–LUMO energy gap.