Formation of Ground State Triplet Diradicals from Annulated Rosarin Derivatives by Triprotonation

Abstract

Annulated rosarins, beta,beta-bridged hexaphyrin(1.0.1.0.1.0) derivatives 1-3, are formally 24 pi-electron antiaromatic species. At low temperature, rosarins 2 and 3 are readily triprotonated in the presence of trifluoroacetic acid in dichloromethane to produce ground state triplet diradicals, as inferred from electron paramagnetic resonance (EPR) spectral studies. From an analysis of the fine structure in the EPR spectrum of triprotonated rosarin H(3)3(3+), a distance of 3.6 angstrom between the two unpaired electrons was estimated. The temperature dependence of the singlet-triplet equilibrium was determined by means of an EPR titration. Support for these experimental findings came from calculations carried out at the (U)B3LYP/6-31G* level, which served to predict a very low-lying triplet state for the triprotonated form of a simplified model system 1.