Identification of a Stable Zn(II) -Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O2 at Room Temperature.

Although a terminal oxyl species bound to certain metal ions is believed to be the intermediate for various oxidation reactions, such as O-O bond generation in photosystem II (PSII), such systems have not been characterized. Herein, we report a stable Zn(II) -oxyl species induced by an MFI-type zeolite lattice and its reversible reactivity with O2 at room temperature. Its intriguing characteristics were confirmed by in situ spectroscopic studies in combination with quantum-chemical calculations, namely analyses of the vibronic Franck-Condon progressions and the ESR signal features of both Zn(II) -oxyl and Zn(II) -ozonide species formed during this reversible process. Molecular orbital analyses revealed that the reversible reaction between a Zn(II) -oxyl species and an O2 molecule proceeds via a radical O-O coupling-decoupling mechanism; the unpaired electron of the oxyl species plays a pivotal role in the O-O bond generation process.