Photophysics of novel 22! porphyrinoids

Abstract

The photophysical properties of toluene solutions of two new 22π expanded porphycene compounds were measured using a combination of various steady-state and time-resolved techniques. The determined triplet energy (ET= 109 ± 3) kJ.mol⁻¹, coincident with the calculated ET = (96.0 ± 10) kJ.mol⁻¹, of both red absorbing compounds is higher than the energy required to excite ground state molecular oxygen to singlet molecular oxygen. However, the intersystem crossing yield is very low (ca. 10⁻²), which makes these compounds poor photosensitizers. The triplet state yield of the two expanded 22π porphyrinoid compounds is much lower than that of the parent porphycene, whereas their fluorescence is as high (ca. 30%) as the value for porphycene. The slower than diffusional quenching rate constant of a porphycene triplet state by the two new compounds reflects a steric hindering factor of the exothermic energy transfer.