Electron Delocalization in a Rigid Cofacial Naphthalene-1,8:4,5-bis(dicarboximide) Dimer

Investigating through-space electronic communication between discrete cofacially oriented aromatic pi-systems is fundamental to understanding assemblies as diverse as double-stranded DNA, organic photovoltaics and thin-film transistors. A detailed understanding of the electronic interactions involved rests on making the appropriate molecular compounds with rigid covalent scaffolds and pi-pi distances in the range of ca. 3.5 angstrom. Reported herein is an enantiomeric pair of doubly-bridged naphthalene-1,8:4,5-bis(dicarboximide) (NDI) cyclophanes and the characterization of four of their electronic states, namely 1) the ground state, 2) the exciton coupled singlet excited state, 3) the radical anion with strong through-space interactions between the redox-active NDI molecules, and 4) the diamagnetic diradical dianion using UV/Vis/NIR, EPR and ENDOR spectroscopies in addition to X-ray crystallography. Despite the unfavorable Coulombic repulsion, the singlet diradical dianion dimer of NDI shows a more pronounced intramolecular pi-pi stacking interaction when compared with its neutral analog.