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Identification of a Stable Zn II –Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O 2 at Room Temperature
Author(s) -
Oda Akira,
Ohkubo Takahiro,
Yumura Takashi,
Kobayashi Hisayoshi,
Kuroda Yasushige
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702570
Subject(s) - chemistry , reactivity (psychology) , unpaired electron , photochemistry , zeolite , molecule , radical , metal , electron paramagnetic resonance , inorganic chemistry , catalysis , organic chemistry , nuclear magnetic resonance , medicine , alternative medicine , pathology , physics
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 O 2 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 O 2 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.