Synthesis of Supramolecular A8Bn Miktoarm Star Copolymers by Host‐Guest Complexation

Nitta, Natsumi; Kihara, Sorin; Haino, Takeharu

doi:10.1002/anie.202219001

Cited by 6 publications

(4 citation statements)

References 71 publications

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“…In bulk state, the diffusion of polymer chains is basically hindered and only local chain/ligand arrangement is allowed, enabling the homogeneous, molecular‐scale blending of high‐entropy polymers (such as the ternary MSP in Figure 1b). [2b] …”

Section: Methodsmentioning

confidence: 99%

Modulating Ligand‐Exchange Dynamics on Metal‐Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

Lai,

He,

Xue

et al. 2023

Angew Chem Int Ed

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The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ~ 2 nm metal‐organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu2+, are applied as templates for the precise synthesis of 24‐arm MSPs for their unique logarithmic ligand exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu2+ to afford corresponding 24‐arm star homo‐polymers, respectively. MSPs can be obtained by mixing targeted homo‐arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned via the recipe of the inputted star polymer mixtures. Interestingly, the obtained MSPs can be sorted into homo‐arm star polymers through a typical solvent extraction protocol. The hybridization and sorting process can be reversibly conducted via the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems.

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Section: Methodsmentioning

confidence: 99%

Modulating Ligand‐Exchange Dynamics on Metal‐Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

Lai,

He,

Xue

et al. 2023

Angew Chem Int Ed

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“…Thus, supramolecular A 8 B n (n = 1,2,4) miktoarm star copolymers PS 8 -H9bCu • G9-G11-PMA can be constructed by host-guest complexation of polymer capsules PS 8 -H9bCu and PMA-attached guest polymers PMA-G9-G11 (Figure 8). [101] Mixing capsules PS 8 -H9bCu and guest polymer PMA-G9 showed slow complexation in solution at ambient temperature, producing the supramolecular A 8 B 1 star copolymer PS 8 -H9bCu • G9-PMA. The host-guest complexation between the capsule and guest units took more than two days due to a high activation free energy of 86 � 5 kJ mol À 1 .…”

Section: Supramolecular a 8 B N Miktoarm Star Copolymers Formed Via M...mentioning

confidence: 99%

“…Thus, supramolecular A 8 B n (n=1,2,4) miktoarm star copolymers PS 8 ‐ H9bCu ⋅ G9‐G11 ‐PMA can be constructed by host‐guest complexation of polymer capsules PS 8 ‐ H9bCu and PMA‐attached guest polymers PMA‐ G9 ‐ G11 (Figure 8). [101] …”

Section: Synthesis Of Supramolecular Star Polymers Using Coordination...mentioning

confidence: 99%

Supramolecular Synthesis of Star Polymers

Haino,

Nitta

2024

ChemPlusChem

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Supramolecular polymers, in which monomers are assembled via intermolecular interactions, have been extensively studied. The fusion of supramolecular polymers with conventional polymers has attracted the attention of many researchers. In this review article, the recent progress in the construction of supramolecular star polymers, including regular star polymers and miktoarm star polymers, is discussed. The initial sections briefly provide an overview of the conventional classification and synthesis methods for star polymers. Coordination‐driven self‐assembly was investigated for the supramolecular synthesis of star polymers. Star polymers with multiple polymer chains radiating from metal–organic polyhedra (MOPs) have also been described. Particular focus has been placed on the synthesis of star polymers featuring supramolecular cores formed through hydrogen‐bonding‐directed self‐assembly. After describing the synthesis of star polymers based on host–guest complexes, the construction of miktoarm star polymers based on the molecular recognition of coordination capsules is detailed.

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“…Star copolymers (SCPs) are non-linear macromolecules with more than two linear polymer chains (arms) with a central core [ 1 , 2 ]. Among SCPs, homogeneous arms (e.g., homopolymer, random, or block copolymer segments) and heterogeneous arms (i.e., miktoarm SCPs (μ-SCPs)) are the two major classes of SCPs [ 3 , 4 ]. The former consists of arms with identical chemical structures, chain ends, and comparable compositions and molecular weights (MWs).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of PDMS-μ-PCL Miktoarm Star Copolymers by Combinations (Є) of Styrenics-Assisted Atom Transfer Radical Coupling and Ring-Opening Polymerization and Study of the Self-Assembled Nanostructures

Huang,

Ejeta,

Lin

et al. 2023

Nanomaterials

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Due to their diverse and unique physical properties, miktoarm star copolymers (μ-SCPs) have garnered significant attention. In our study, we employed α-monobomoisobutyryl-terminated polydimethylsiloxane (PDMS-Br) to carry out styrenics-assisted atom transfer radical coupling (SA ATRC) in the presence of 4-vinylbenzyl alcohol (VBA) at 0 °C. By achieving high coupling efficiency (χc = 0.95), we obtained mid-chain functionalized PDMS-VBAm-PDMS polymers with benzylic alcohols. Interestingly, matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis revealed the insertion of only two VBA coupling agents (m = 2). Subsequently, the PDMS-VBA2-PDMS products underwent mid-chain extensions using ε-caprolactone (ε-CL) through ring-opening polymerization (ROP) with an efficient organo-catalyst at 40 °C, resulting in the synthesis of novel (PDMS)2-μ-(PCL)2 μ-SCPs. Eventually, novel (PDMS)2-μ-(PCL)2 μ-SCPs were obtained. The obtained PDMS-μ-PCL μ-SCPs were further subjected to examination of their solid-state self-assembly through small-angle X-ray scattering (SAXS) experiments. Notably, various nanostructures, including lamellae and hexagonally packed cylinders, were observed with a periodic size of approximately 15 nm. As a result, we successfully developed a simple and effective reaction combination (Є) strategy (i.e., SA ATRC-Є-ROP) for the synthesis of well-defined PDMS-μ-PCL μ-SCPs. This approach may open up new possibilities for fabricating nanostructures from siloxane-based materials.

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Synthesis of Supramolecular A₈B_n Miktoarm Star Copolymers by Host‐Guest Complexation

Cited by 6 publications

References 71 publications

Modulating Ligand‐Exchange Dynamics on Metal‐Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

Modulating Ligand‐Exchange Dynamics on Metal‐Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

Supramolecular Synthesis of Star Polymers

Synthesis of PDMS-μ-PCL Miktoarm Star Copolymers by Combinations (Є) of Styrenics-Assisted Atom Transfer Radical Coupling and Ring-Opening Polymerization and Study of the Self-Assembled Nanostructures

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