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Journal ArticleDOI

Activating catalysts with mechanical force

TLDR
It is found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution and ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions.
Abstract
Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.

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Citations
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Journal ArticleDOI

Stimuli-responsive supramolecular polymeric materials.

TL;DR: This critical review of recent developments in supramolecular polymeric materials is addressed, which can respond to appropriate external stimuli at the fundamental level due to the existence of noncovalent interactions of the building blocks.
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Using the dynamic bond to access macroscopically responsive structurally dynamic polymers

TL;DR: The emergence of a new trend in the design of adaptive materials that involves the use of reversible chemistry to programme a response that originates at the most fundamental (molecular) level is described.
Journal ArticleDOI

Self-healing polymers and composites

TL;DR: A survey of self-healing polymers can be found in this article, where the authors review the major successful autonomic repairing mechanisms developed over the last decade and discuss several issues related to transferring these selfhealing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality.
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Mechanically-induced chemical changes in polymeric materials

TL;DR: The purpose of this review is to broadly survey the mechanical to chemical relationships between synthetic polymers, and to consider the I-O relationship as an energy transduction process for designing stimuli-responsive materials.
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Covalent adaptable networks: smart, reconfigurable and responsive network systems.

TL;DR: A tutorial review on covalent adaptable networks (CANs), in which covalently crosslinked networks are formed such that triggerable, reversible chemical structures persist throughout the network, and how the application of a stimulus causes these materials to alter their shape, topography, and properties is provided.
References
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Journal ArticleDOI

The Development of L2X2RuCHR Olefin Metathesis Catalysts: An Organometallic Success Story

TL;DR: The discussion includes an analysis of trends in catalyst activity, a description of catalysts coordinated with N-heterocyclic carbene ligands, and an overview of ongoing work to improve the activity, stability, and selectivity of this family of L2X2Ru=CHR complexes.
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N‐Heterocyclic Carbenes as Organocatalysts

TL;DR: This work highlights the ever-increasing number of reactions that can be promoted by N-heterocyclic carbenes and investigates the role of benzoin condensation in these reactions.
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Mechanochemistry: the mechanical activation of covalent bonds.

TL;DR: A survey of the classical works in mechanochemistry is given and the key mechanochemical phenomena into perspective with recent results from atomic force microscopy and quantum molecular dynamics simulations are put into perspective.
Journal ArticleDOI

Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts

TL;DR: The origins of the observed substituent effects as well as the implications of these studies for the design and implementation of new olefin metathesis catalysts and substrates are discussed in detail.
Journal ArticleDOI

Biasing reaction pathways with mechanical force

TL;DR: It is shown that mechanically sensitive chemical groups make it possible to harness the mechanical forces generated when exposing polymer solutions to ultrasound, and that this allows us to accelerate rearrangement reactions and bias reaction pathways to yield products not obtainable from purely thermal or light-induced reactions.
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