To gain insight into the singlet oxygen (1O2) generation properties of supramolecular complexes of cyclic free-base porphyrin dimer with fullerene C60, we evaluated the 1O2 quantum yield (ΦΔ) and rate constant (Kobs) of 1O2 generation for a cyclic free-base porphyrin dimer (CPD) linked by butadiyne bearing four 4-pyridyl groups and its inclusion complex (C60⊂CPD) with C60. We demonstrate that CPD and C60⊂CPD possess the ability to generate 1O2 under visible light irradiation. Moreover, it was found that the ΦΔ value of C60⊂CPD is lower than that of CPD. Based on the kinetic and thermodynamic consideration concerning the electron transfer processes between the porphyrin dimer and C60, this work revealed that the lower ΦΔ value of the C60 inclusion complex would be attributed to the formation of the charge-separated state c60·−-CPD·+, leading to a low intersystem crossing (ISC) efficiency for the formation of the triplet excited state 3(CPD)*.
All Science Journal Classification (ASJC) codes
- Chemical Engineering(all)