Construction and morphology of non-covalently double-crosslinked supramolecular polymer networks

Chen, Senbin; Wang, Ke; Zhang, Geng; Chen, Yu; Zheng, Xihuang; Wang, Huiying; Zhu, Jintao

doi:10.1039/c9py00681h

Cited by 4 publications

(3 citation statements)

References 42 publications

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“…Aggregation of hydrogen‐bonded helical structures by complementary interactions has been exploited to construct hierarchical [39,40,51–53] or competitive [54] supramolecular aggregates with tunable chiroptical properties. The orthogonality of hydrogen bonding and metal‐ligand interactions also allowed the construction of crosslinked supramolecular polymer networks, yet the impact of chirality was not probed in this system [55] . Overall, it is not clear how the chiral induction ability of the “sergeant” is affected by the aggregation process.…”

Section: Introductionmentioning

confidence: 98%

“…The orthogonality of hydrogen bonding and metal-ligand interactions also allowed the construction of crosslinked supramolecular polymer networks, yet the impact of chirality was not probed in this system. [55] Overall, it is not clear how the chiral induction ability of the "sergeant" is affected by the aggregation process. As lateral aggregation of supramolecular polymers can be achieved by various mechanisms, such as van der Waals or directional metal-ligand interactions between polymer side chains, it would be interesting to probe and rationalize the influence of aggregation on the extent of the S&S effect in hydrogen-bonded helices.…”

Section: Introductionmentioning

confidence: 99%

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Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Hammoud

Martínez‐Aguirre

et al. 2023

Chemistry A European J

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Aggregation of supramolecular helices, for example through interdigitation of their alkyl side chains or through more directional supramolecular interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the "sergeant") is introduced as a minor component in these assemblies composed of a majority of achiral monomers (the "soldiers"), it is not clear how the aggregation changes the ability of the sergeant to induce a preferential helicity to the polymer main chain (the so-called "sergeants-and-soldiers" effect). This study reports a detailed investigation of the influence of [Cu(OAc) 2 •H 2 O] coordination on the structure and chiroptical properties of helical hydrogen-bonded co-assemblies composed of a catalytically-active benzene-1,3,5-tricarboxamide (BTA) monomer, acting as the "soldier", and an enantiopure BTA monomer derived from cyclohexylalanine, playing the role of the "sergeant". The copper actually significantly influences the extent of the "sergeants-and-soldiers" effect since it acts as a crosslink that induces some chiral defects in the supramolecular helices. These crosslinks appear to be preserved during the catalytic hydrosilylation of 4-nitroacetophenone. The aggregation of helices through the formation of copper crosslinks is reversible since homochiral single helices are exclusively formed in the case of sergeant-rich assemblies. The fact that both main chain and side chain aggregation affects the chiroptical properties of supramolecular helices must be considered in the design of elaborated chiral materials.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Hammoud

Martínez‐Aguirre

et al. 2023

Chemistry A European J

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“…To suppress macrophase separation and to induce the formation of homogeneous phases, noncovalent interactions such as halogen bonds, [23][24][25] hydrogen bonds, [26][27][28][29][30][31] ion-dipole, or π-π interactions between the different polymers are often utilized. [32] Halogen-bonds play a significant role as a noncovalent interaction especially in crystal engineering, however, are arguably one of the least exploited supramolecular forces for forming macromolecular-based assemblies.…”

Section: Introductionmentioning

confidence: 99%

Halogen‐Bond Mediated 3D Confined Assembly of AB Diblock Copolymer and C Homopolymer Blends

Zheng

Ren

Wang

et al. 2021

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Halogen‐bond driven assembly, a world parallel to hydrogen‐bond, has emerged as an attractive tool for constructing (macro)molecular arrangement. However, knowledge about halogen‐bond mediated confined‐assembly in emulsion droplets is limited so far. An I….N bond mediated confined‐assembly pathway to enable order‐order phase transitions is reported here. Compared to hydrogen bonds, the distinct features of halogen bonds (e.g., higher directionality, hydrophobicity, favored in polar solvents), offers opportunities to achieve novel nanostructures and materials. Polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) AB diblock copolymer is chosen as halogen acceptor, while an iodotetrafluorophenoxy substituted C‐type homopolymer, (poly(3‐(2,3,5,6‐tetrafluoro‐4‐iodophenoxy)propyl acrylate), PTFIPA) is designed as halogen donor, synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization. Formation of halogen bonding donor–acceptor pairs between the PTFIPA homopolymer and the P4VP segments presented in PS‐b‐P4VP, increase the volume of P4VP domains, in turn inducing an order‐to‐order morphology transition sequence: changing from spherical → cylindrical → lamellar → inverse cylindrical, by tuning the PTFIPA content and choice of surfactant. Subsequent selective swelling/deswelling of the P4VP domains give rise to further internal morphology transitions, creating tailored mesoporous microparticles, disassembled nanodiscs, and superaggregates. It is believed that these results will stimulate further examinations of halogen bonding interactions in emulsion droplets and many areas of application.

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Supramolecular Polymers, Formed by Orthogonal Non‐covalent Interactions*

2021

Supramolecular Polymers and Assemblies

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Construction and morphology of non-covalently double-crosslinked supramolecular polymer networks

Abstract: A straightforward synthesis of α-Ba, ω-TAP functionalized polymers, Ba-PnBuA-TAP, is reported, leading to the formation of double-crosslinked supramolecular networks driven via the sequential hydrogen-bonding association and metal-coordination.

Cited by 4 publications

References 42 publications

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Halogen‐Bond Mediated 3D Confined Assembly of AB Diblock Copolymer and C Homopolymer Blends

Supramolecular Polymers, Formed by Orthogonal Non‐covalent Interactions*

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