Stress-responsive properties of metallocenes in metallopolymers

Sha, Ye; Zhang, Hao; Zhou, Zhou; Luo, Zhenyang

doi:10.1039/d1py00311a

Cited by 23 publications

(21 citation statements)

References 116 publications

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“…If the cage cleavage involves heterolytic dissociation for a certain bond, the dissociation energy would include a contribution from the charge separation of that specific bond in the relative low dielectric THF solvent. Then, tetrabutylammonium bromide salt was added to the sonication mixture of P1 to stabilize the charge separation [6r, 7, 12] . However, the chain scission rate proved unaffected as shown in Figure S4.…”

Section: Methodsmentioning

confidence: 99%

The Mechanochemistry of Carboranes

et al. 2022

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We developed o-carborane as a new mechanophore by showing that the o-carborane cluster is the preferred scission site in chain-centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry (m-carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation.

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Section: Methodsmentioning

confidence: 99%

The Mechanochemistry of Carboranes

et al. 2022

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“… Metallocenes are unique mechanophores undergoing several intramolecular changes. This depends on the magnitude of force exerted on the system [2c] …”

Section: Metallopolymer‐based Systemsmentioning

confidence: 99%

“…In recent years, a new class of mechanophores has been developed, using various metallocene derivatives in main‐chain polymers to undergo bond scission, cumulating in metal ion release (Figure 14 ). [2c] …”

Section: Metallopolymer‐based Systemsmentioning

confidence: 99%

Release of Molecular Cargo from Polymer Systems by Mechanochemistry

Küng

Göstl

Schmidt

2022

Chemistry A European J

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The design and manipulation of (multi)functional materials at the nanoscale holds the promise of fuelling tomorrow's major technological advances. In the realm of macromolecular nanosystems, the incorporation of force‐responsive groups, so called mechanophores, has resulted in unprecedented access to responsive behaviours and enabled sophisticated functions of the resulting structures and advanced materials. Among the diverse force‐activated motifs, the on‐demand release or activation of compounds, such as catalysts, drugs, or monomers for self‐healing, are sought‐after since they enable triggering pristine small molecule function from macromolecular frameworks. Here, we highlight examples of molecular cargo release systems from polymer‐based architectures in solution by means of sonochemical activation by ultrasound (ultrasound‐induced mechanochemistry). Important design concepts of these advanced materials are discussed, as well as their syntheses and applications.

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“…Numerous sequence-controlled polymerization methodologies based on chemical approaches have been established to prepare organic sequence-controlled polymers. − One of the most straightforward among these methods may be the direct transformation of tailor-made monomers with a built-in sequence into polymer products. Most of these polymerization strategies are anionic polymerizations and metathesis polymerizations, e.g., ring-opening metathesis polymerization (ROMP) − and acyclic diene metathesis (ADMET) polymerization, , which are also the methods of choice for the preparation of metallopolymers due to their good tolerance toward various functionalities. − …”

Section: Introductionmentioning

confidence: 99%

Sequence-Controlled Metallopolymers: Synthesis and Properties

et al. 2021

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Sequence-controlled organometallic polymers are prepared by regioselective ring-opening metathesis polymerization (ROMP) of multiple-substituted cyclooctene monomers with a built-in sequence of the metal-containing substituents. The side-chain metal functions of these metallopolymers are consist of metallocenes, i.e., ferrocene and ruthenocene. The photophysical, thermal, and electrochemical properties can be finely tailored by the metallocene sequence along the polymer chain. This work provides fundamental understanding to unveil the structure–property relationship of sequence-controlled metallopolymers. This highly efficient chain-growth polymerization is expected to incorporate a variety of metal moieties into a single organometallic polymer with site specificity, architectural complexity, and functional versatility. The new sequence-controlled metallopolymers are expected to provide access to materials with potential applications for electrochemical sensing, information processing, and magnetic materials.

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Stress-responsive properties of metallocenes in metallopolymers

Abstract: In this review, we focus on metallocenes (e.g., ferrocene, ruthenocene, cobaltocene/cobaltocenium, etc.), a class of prototypical organometallic compounds, as emerging stress-responsive building blocks for materials. In particular, they are used...

Cited by 23 publications

References 116 publications

The Mechanochemistry of Carboranes

The Mechanochemistry of Carboranes

Release of Molecular Cargo from Polymer Systems by Mechanochemistry

Sequence-Controlled Metallopolymers: Synthesis and Properties

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