Photolysis of endoperoxides in the presence of nitroxides: a laser flash photolysis study with optical and ESR detection

Time-resolved electron paramagnetic resonance spectroscopy, transient absorption, and phosphorescence spectroscopy were used to investigate the spin polarization of a nitroxide free radical induced by interaction with singlet oxygen (1O2). The latter was generated by photolysis of endoperoxides of two anthracene derivatives. Although both anthracene endoperoxides are structurally similar, opposite spin polarization of the nitroxide was observed. Photolysis of one endoperoxide leads to absorptive nitroxide spin polarization due to interaction with the generated 1O2. Photolysis of the other endoperoxide generated emissive nitroxide spin polarization, probably due to interaction of the endoperoxide triplet states with nitroxides.