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Visible-Light-Controlled Reaction-Separation for Asymmetric Sulfoxidation in Water with Photoresponsive Metallomicelles

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journal contribution
posted on 21.10.2019, 20:44 by Zhiyang Tang, Weiying Wang, Yibing Pi, Jiajun Wang, Chaoping Li, Rong Tan, Donghong Yin
Metallomicellar catalysis has gained increasing attention in recent years since it made water-incompatible organometallic catalysis highly efficient in water. However, a convenient approach to combine activity and recovery of metallomicelles from aqueous systems has remained challenging to date. Herein, we developed a series of nitrospiropyran-containing metallomicelles which possessed visible-light-responsivity, to realize the visible-light-controlled reaction and separation for asymmetric sulfoxidation in water. A series of nitrospiropyran-containing diblock chiral salen TiIV copolymers were thus prepared by copolymerizing photosensitive nitrospiropyran derivative with hydrophobic chiral salen TiIV monomer via free-radical polymerization. Characterization results suggested their visible-light-controlled self-assembly behavior in water due to the negative photochromism of nitrospiropyran block. The resultant light-responsive metallomicelles induced a micellar catalysis approach in the dark for asymmetric sulfoxidation in water using H2O2 as an oxidant, leading to significant rate acceleration and remarkable high selectivity over a wide range of aryl alkyl sulfides. When exposed to visible light, they were collapsed and precipitated from the aqueous system for easy recycling. The visible-light-controlled reaction-separation approach provided an efficient way to combine activity and recovery of metallomicelles in aqueous asymmetric catalysis, which was a benefit for energy-saving and industrial applications.