In the presently known mechanisms of photoacidity the molecular orbitals of the electronic transition that lead to the photoacidic character are (partially) localized on the proton donating moiety. The mechanistic interpretations based on charge distribution and excited state antiaromaticity are of this category. In this case, we argue that a novel mechanism may be operative, where electrostatic through-space interactions act as the driving force for the photoacidity of tw-HDMAPAN.