B–H_b⋯π interactions in the complexes formed between boranes (diborane-6, tetraborane-10 and pentaborane-9) and a model graphene (coronene) system are studied in the light of density functional theory. Stabilization energies are calculated and the complexes are predicted to be stable in both gas and solvent phases. Thermochemical analysis also predicts the feasibility of such complexes. The presence of dopants such as N/B/BN on the coronene moiety significantly affects the stabilization energy of the complexes depending upon the number of dopants. The HOMO energy of the complexes successfully predicts their stability. The presence of a solvent phase does not impart any substantial effect on the stability of the complex formed. The absorption spectra of the free coronene units (undoped/doped) and their respective complexes are found to be similar.