Porphycene (PC), a structural isomer of porphine, is a promising photosensitizer for photodynamic therapy. Its excited states can be quenched by molecular oxygen, generating singlet O2. The electronic structures of PC and of the PC⋯O2 complex were investigated using complete active space perturbation theory. It is shown that singlet oxygen generation involves 12 electronic states of the complex, with singlet, triplet, and quintet multiplicities. Two scenarios for singlet-O2 yield are analyzed: (I) quenching of triplet states of PC and (II) quenching of singlet states of PC. In the first scenario, which is favored under low O2 concentration, singlet-O2 yield is limited by the relatively low triplet quantum yield of PC. We discuss how the singlet-O2 yield would be busted if conditions for occurrence of the second scenario could be achieved.
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