Substituent‐Dependent Photoexcitation Processes of π‐Stacked Ion Pairs

Abstract

Porphyrin ion pairs, the charge of which is delocalized in core units, form tightly associated structures through i π-i π interactions. 5,10,15-Triphenyl-substituted porphyrin-Au III complex, which is favorable for forming stacked structures in the form of a stable ion, has been synthesized. Ion-pair metathesis based on the hard and soft acids and bases theory enabled combination with porphyrin anions possessing electronic states controlled by electron-donating and electron-withdrawing groups. Transient absorption spectroscopy suggested that the lifetimes of the radical pairs generated by photoinduced electron transfer of the ion pairs could be controlled by a judicious combination of the anions and cations.

π-Electronic ion pairs: building blocks for supramolecular nanoarchitectonics viaiπ–iπ interactions

“…These findings suggest application potential of these ion pairs in photocatalysis owing to their tuneable electronic state. 6,53…”

“…13a). 6,50–53 Thus, porphyrin Au III complexes readily form ion pairs in combination with desired anions and can be adopted as building blocks for π-electronic ion-pairing assemblies. 6,52…”