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A Designed TEMPO‐derivate Catalyst with Switchable Signals of EPR and Photoluminescence: Application in the Mechanism of Alcohol Oxidation
Author(s) -
Yin Lu,
Zhang Jiaxiang,
Yao Jia,
Li Haoran
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201800345
Subject(s) - electron paramagnetic resonance , photoluminescence , terpyridine , diamagnetism , alcohol oxidation , catalysis , paramagnetism , photochemistry , chemistry , benzyl alcohol , alcohol , radical , materials science , organic chemistry , nuclear magnetic resonance , metal , physics , optoelectronics , quantum mechanics , magnetic field
Construction the in situ, real‐time monitoring methodology for chemical changes, especially in the mechanism of oxidation, has long been regarded as a significant and challenging concern. Herein, we designed and synthesized a TEMPO‐mediated alkynylplatinum(II) terpyridine complex with switchable activity in photoluminescence and EPR (Electron Paramagnetic Resonance) spectra. This complex of alkynylplatinum(II) terpyridine‐TEMPO [(2, 2,6,6‐tetramethylpiperidin‐1‐yl)oxyl] is paramagnetic, while the in situ formed alkynylplatinum(II) terpyridine‐TEMPOH is diamagnetic, so that concentration changes of TEMPO/ TEMPOH species were obtained successfully by photoluminescence and EPR spectra in an operando way. As a model example, we investigated the mechanism of alcohol oxidation mediated by TEMPO/ bis(acetoxy)iodo]benzene (BAIB). It was found that, with the consumption of co‐oxidant (BAIB), the concentration and conformation of catalyst (TEMPO) were changed gradually, and the vital role of catalyst and co‐oxidant in the benzyl alcohol oxidation was clearly showed by photoluminescence and EPR spectroscopies. On the basis of these observations, we suggested an effective methodology to study the mechanism of chemical reaction, which is promising for further practical applications in analytical or environmental issues.