Cation Template‐Assisted RAFT Cyclopolymerization of Hexa(Ethylene Glycol) Di(meth)acrylates to Thermoresponsive Pseudo‐Crown Ether Polymers

Kimura, Yoshihiko; Terashima, Takaya

doi:10.1002/marc.202000670

“…From the viewpoint of monomer structure, the use of a rigid structure with low molecular mobility and the immobilization of two polymerizable groups on the adjacent position are the important keys to construct the monomer design. In addition, the suppression of the conformational change of monomer structure promotes cyclopolymerization. , Recently, cyclopolymerization systems based on template polymerization using the metal ion capture of bifunctional monomers as a driving force have been reported. − …”

Section: Introductionmentioning

confidence: 99%

Radical Cyclopolymerization of Isocyanurate Core-Based Bifunctional Monomers Bearing a Hydroxy Group and Their Application to Cross-Linking Reaction

Okamoto

¹

,

Furusho

²

,

Endō

³

2022

ACS Appl. Polym. Mater.

0

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We report the synthesis of linear polymers having macrocyclic units in the main chain and hydroxy groups in the side chains by radical cyclopolymerization of the isocyanurate core-based bifunctional monomers and their utilization to cross-linking reaction via esterification. The 5% weight loss temperature (T d5 ) and glass transition temperature (T g ) of the resulting linear polymers have clearly revealed the effect of the introduced macrocyclic unit upon the thermal stability of the polymer. Among the synthesized cross-linked polymers, the rigidity of the incorporated cross-linked structure in the cross-linked polymers also dominates thermal properties of polymers. Such reactive linear polymers including macrocyclic units and hydroxy groups are expected to be applied to various fields of high thermal-resistance materials.

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Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen

Stoy,

Jürgensen,

Millidoni

et al. 2023

Angewandte Chemie

0

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Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate novel structural motifs in an operationally simple approach, which are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p‐block elements, albeit heavier p‐block elements show low bond dissociation energies and appear to be ideally suited for this approach. Here we show that a dinuclear organometallic bismuth compound, containing BiMe2 groups that are connected by a thioxanthene linker, readily undergoes selective and reversible cleavage of its Bi–C bonds upon exposure to external stimuli. The exploitation of DCvC in the field of organometallic heavy p‐block chemistry grants access to unprecedented macrocyclic and barrel‐type oligonuclear compounds.

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Bismuth in Dynamic Covalent Chemistry: Access to a Bowl‐Type Macrocycle and a Barrel‐Type Heptanuclear Complex Cation

Stoy,

Jürgensen,

Millidoni

et al. 2023

Angew Chem Int Ed

3

0

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Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate novel structural motifs in an operationally simple approach, which are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p‐block elements, albeit heavier p‐block elements show low bond dissociation energies and appear to be ideally suited for this approach. Here we show that a dinuclear organometallic bismuth compound, containing BiMe2 groups that are connected by a thioxanthene linker, readily undergoes selective and reversible cleavage of its Bi–C bonds upon exposure to external stimuli. The exploitation of DCvC in the field of organometallic heavy p‐block chemistry grants access to unprecedented macrocyclic and barrel‐type oligonuclear compounds.

show abstract

Cation Template‐Assisted RAFT Cyclopolymerization of Hexa(Ethylene Glycol) Di(meth)acrylates to Thermoresponsive Pseudo‐Crown Ether Polymers

Cited by 3 publications

References 35 publications

Radical Cyclopolymerization of Isocyanurate Core-Based Bifunctional Monomers Bearing a Hydroxy Group and Their Application to Cross-Linking Reaction

Radical Cyclopolymerization of Isocyanurate Core-Based Bifunctional Monomers Bearing a Hydroxy Group and Their Application to Cross-Linking Reaction

Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen

Bismuth in Dynamic Covalent Chemistry: Access to a Bowl‐Type Macrocycle and a Barrel‐Type Heptanuclear Complex Cation

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