Highly Efficient Supramolecular Catalysis by Endowing the Reaction Intermediate with Adaptive Reactivity

Jiao, Yang; Tang, Bohan; Zhang, Yucheng; Xu, Jiang‐Fei; Wang, Zhiqiang; Zhang, Xi

doi:10.1002/anie.201713351

Cited by 49 publications

(29 citation statements)

References 70 publications

(7 reference statements)

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“…The proposed first step is the oxidation of TEMPO and the formation of key cationic intermediate (TEMPO + ), which can undergo unwanted side reactions in water. The use of a supramolecular TEMPO/CB[7] complex resulted in higher conversion to the corresponding aldehyde as a consequence of the electrostatic stabilization of TEMPO + (Jiao et al, 2018).…”

Section: Confinement Effects In Homogeneous Catalysismentioning

confidence: 99%

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

et al. 2018

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This review focuses on the effects that confinement of molecular and heterogeneous catalysts with well-defined structure has on the selectivity and activity of these systems. A general introduction about catalysis and how the working principles of enzymes can be used as a source of inspiration for the preparation of catalysts with enhanced performance is provided. Subsequently, relevant studies demonstrate the importance of second coordination sphere effects in a broad sense (in homogeneous and heterogeneous catalysis). Firstly, we discuss examples involving zeolites, MOFs and COFs as heterogeneous catalysts with well-defined structures where confinement influences catalytic performance. Then, specific cases of homogeneous catalysts where non-covalent interactions determine the selectivity and activity are treated in detail. This includes examples based on cyclodextrins, calix[n]arenes, cucurbit[n]urils, and self-assembled container molecules. Throughout the review, the impact of confined spaces is emphasized and put into context, in order to get a better understanding of the effects of confinement on catalyst performance. In addition, this analysis intends to showcase the similarities between homogeneous and heterogeneous catalysts, which may aid the development of novel strategies.

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Section: Confinement Effects In Homogeneous Catalysismentioning

confidence: 99%

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

et al. 2018

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“…22 On the other hand, the stability of radicals can be reversibly controlled and radicals can also respond to external stimuli, thus providing novel possibilities, such as switchable properties, smart functional materials and adaptive radical systems. [23][24][25] In general, the principles of tuning the stability of organic radicals can be summarized as steric protection and tuning the delocalization of spin density. 15,16,26 In this perspective article, we will introduce covalent approaches and non-covalent approaches to modulate the stability of radicals from the viewpoint of these two principles (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Tuning the stability of organic radicals: from covalent approaches to non-covalent approaches

et al. 2020

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“…On the one hand, the host provides a confined space and independent microenvironment to enhance charge transfer interaction for improved ISC efficiency. On the other hand, the host‐guest complex benefits from the well‐defined structure, considerable solubility and adequate dynamicity to ensure the contact of the triplet state guest with other reactants, thus facilitating energy transfer and electron transfer [41–54] . To this end, N,N’‐dimethyl 2,5‐bis(4‐pyridinium)thiazolo[5,4‐d]thiazole diiodide (MPT), an efficient fluorochrome with acceptor‐donor‐acceptor structure, was designed [55] .…”

Section: Methodsmentioning

confidence: 99%

Transforming a Fluorochrome to an Efficient Photocatalyst for Oxidative Hydroxylation: A Supramolecular Dimerization Strategy Based on Host‐Enhanced Charge Transfer

Tang

et al. 2021

Angewandte Chemie

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The development of non‐covalent synthetic strategy to fabricate efficient photocatalysts is of great importance in theranostic and organic materials. Herein, a fluorochrome N,N′‐dimethyl 2,5‐bis(4‐pyridinium)thiazolo[5,4‐d]thiazolediiodide (MPT) was transformed into an efficient photocatalyst through supramolecular dimerization in the cavity of cucurbit[8]uril (CB[8]). The host‐enhanced charge transfer interaction within the supramolecular dimer 2MPT‐CB[8] dramatically promoted intersystem crossing to produce triplet. In addition, the staggered conformation of 2MPT‐CB[8] facilitated the energy transfer and electron transfer of the triplet. As a result, 2MPT‐CB[8] could serve as a high‐efficiency photocatalyst for the oxidative hydroxylation of arylboronic acids. This supramolecular dimerization strategy enriches the supramolecular engineering of functional π‐systems. It is anticipated that this strategy can be extended to fabricate various π‐systems with tailor‐made functions.

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Highly Efficient Supramolecular Catalysis by Endowing the Reaction Intermediate with Adaptive Reactivity

Cited by 49 publications

References 70 publications

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

Tuning the stability of organic radicals: from covalent approaches to non-covalent approaches

Transforming a Fluorochrome to an Efficient Photocatalyst for Oxidative Hydroxylation: A Supramolecular Dimerization Strategy Based on Host‐Enhanced Charge Transfer

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