Electron transfer reactions of rigid, cofacially compressed, ir-stacked porphyrin-bridge-quinone systems

摘要

A 1,8-naphthyl pillaring motif can be utilized to enforce sub van der Waals interplanar separations between juxtaposed porphyryl, aromatic bridge, and quinonyl components of donor-spacer-acceptor (D-Sp-A) compounds. Such structures, synthesized via metal-mediated cross-coupling of appropriately functionalized (porphinato)zinc(II), arene, and quinone precursors, manifest unusual conformational rigidity in the condensed phase, and significant electronic communication between the cofacially aligned D, Sp, and A components. NMR experiments provide rigorous determination of the ambient temperature structures of these species in solution, while computational methods offer insight into the fragment molecular orbital interactions that give rise to the strong D-A coupling evident in these assemblies. The distance-, temperature-, and solvent-dependences of photoinduced charge separation (CS) and thermal