The judicial placement of main group elements in conjugated structures is emerging as a key route to novel functional hybrid materials. We demonstrate here that the formation of B-N Lewis pairs at the periphery of anthracene leads to buckling of the backbone while also dramatically lowering the LUMO energy. The resulting BN-substituted contorted poly cyclic aromatic hydrocarbons, show large bathochromic, shifts in the absorption and emission relative to all-carbon analogs. In the presence of light, they rapidly react with O(2 )without the need for, an external photosensitizer, resulting in selective and reversible, formation of the corresponding endoperoxides.