meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26π-electronic circuit can be regarded as a real homolog of porphyrin with an 18π-electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso-hexakis(pentafluorophenyl)hexaphyrin(22.214.171.124.1.1) by deprotonation of the inner N-H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono- and dianions of hexaphyrin display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π-electronic circuit and cause enhanced aromaticity. Circuit tuning: Deprotonation causes significant structural deformations, which give rise to different and more effective π-conjugated circuits that have been found to be responsible for enhanced aromaticity (see figure). This work highlights the potential of the deprotonation strategy for tuning the electronic properties of expanded porphyrins.
All Science Journal Classification (ASJC) codes
- Organic Chemistry