Secondary Structure in Nonpeptidic Supramolecular Block Copolymers

Milton, Margarita; Deng, Ru Wen; Mann, Arielle; Wang, Chengyuan; Tang, Danni; Weck, Marcus

doi:10.1021/acs.accounts.1c00028

Cited by 24 publications

(19 citation statements)

References 74 publications

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“…The Pd(II)-catalyzed living polymerization of isocyanides is a versatile method for the precise synthesis of polyisocyanides with intriguing structures and diverse functions. ,, Although some developments have been achieved, several issues need to be investigated in the future. By incorporating elaborately designed substituents and ligands onto Pd(II) catalysts, more interesting polymers can be anticipated, such as cyclic polymers, ladder polymers, and so on.…”

Section: Discussionmentioning

confidence: 99%

“…Furthermore, a helix can be optically active due to the excess of one-handed helicity because right- and left-handed helices are the enantiomers of each other. With the advances in synthesis methodology, a series of artificial helical polymers were developed, such as polyacetylenes, polyisocyanates, sterically restricted poly(methacrylate ester)s, polychoral, polyguanidines, and polyisocyanides. − Polyisocyanides, in particular, are intriguing due to their rigid helical backbone and numerous applications. − Consequently, the precise synthesis of helical polyisocyanides with defined structures and tunable compositions is highly sought after.…”

Section: Introductionmentioning

confidence: 99%

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Alkyne-Palladium(II)-Catalyzed Living Polymerization of Isocyanides: An Exploration of Diverse Structures and Functions

2021

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Conspectus Inspired by the perfect helical structures and the resulting exquisite functions of biomacromolecules, helical polymers have attracted increasing attention in recent years. Polyisocyanide is well known for its distinctive rodlike helical structure and various applications in chiral recognition, enantiomer separation, circularly polarized luminescence, liquid crystallization, and other fields. Although various methods and catalysts for isocyanide polymerization have been reported, the precise synthesis of helical polyisocyanides with controlled molecular weight, low dispersity, and high tacticity remains a formidable challenge. Owing to a limited synthesis strategy, the controlled synthesis of topological polyisocyanides has barely been realized. This Accounts highlights our recent endeavors to explore novel catalysts for the living polymerization of isocyanides. Fortunately, we discovered that alkyne-Pd(II) catalysts could initiate the living polymerization of isocyanides, resulting in helical polyisocyanides with controlled structures, high tacticity, and tunable compositions. These catalysts are applicable to various isocyanide monomers, including alkyl isocyanides, aryl isocyanides, and diisocyanobenzene derivatives. Incorporating chiral bidentate phosphine ligands onto alkyne-Pd(II) complexes formed chiral Pd(II) catalysts, which promoted the asymmetric living polymerization of achiral isocyanide, yielding single left- and right-handed helices with highly optical activities. Using alkyne-Pd(II) catalysts, various topological polyisocyanides have been facilely prepared, including hybrid block copolymers, bottlebrush polymers, core cross-linked star polymers, and organic/inorganic nanoparticles. For instance, various hybrid block polyisocyanides were easily produced by coupling alkyne-Pd(II)-catalyzed living isocyanide polymerization with controlled radical polymerization and ring-opening polymerization (ROP). Combining the ring-opening metathesis polymerization (ROMP) of norbornene with Pd(II)-catalyzed isocyanide polymerization, bottlebrush polyisocyanides and core cross-linked star polymers were easily prepared. Pd(II)-catalyzed living polymerization of poly(lactic acid)s with isocyanide termini resulted in densely grafted bottlebrush polyisocyanides with closely packed side chains. Moreover, the surface-initiated living polymerization of isocyanides produced a family of polyisocyanide-grafted organic/inorganic hybrid nanoparticles using nanoparticles with alkyne-Pd(II) catalysts anchored on the surfaces. Surprisingly, the nanoparticles and star polymers with helical polyisocyanide arms performed exceptionally well in terms of chiral recognition and resolution. Incorporated organocatalysts such as proline and prolinol units onto the pendants of optically active helical polyisocyanides, a family of polymer-based chiral organocatalysts, were generated, which showed significantly improved stereoselectivity for the asymmetric Aldol reaction and Michael addition and can be easily recycled. Us...

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Alkyne-Palladium(II)-Catalyzed Living Polymerization of Isocyanides: An Exploration of Diverse Structures and Functions

2021

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“…Molecular engineering allows the design of novel materials with a certain structure and specific properties related to it. Within this topic, modelling new helical structures based on non-natural building blocks such as helicenes, [1][2][3] foldamers, [3][4][5][6] supramolecular [7][8][9] or covalent helical polymers, [10][11][12][13][14][15][16][17] has attracted the attention of the scientific community. These studies are inspired by the structure/ function relationships present in biomacromolecules such as peptides, proteins, DNA or polysaccharides.…”

Section: Introductionmentioning

confidence: 99%

Dissymmetric Chiral Poly(diphenylacetylene)s: Secondary Structure Elucidation and Dynamic Luminescence

et al. 2022

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The secondary structure of a dissymmetric and chiral poly(diphenylacetylene) (PDPA) is elucidated by combining the data from NMR experiments (regioregular head to tail structure), Raman and IR studies (E configuration of the polyene double bonds), and high-resolution AFM images (helical pitch, packing angle and orientation of the external helix). As a result, an E-transoidal polyene backbone describing three coaxial helices is obtained. Theoretical electronic circular dichroism (ECD) studies of the structure show a good correspondence between experimental and theoretical data and allow one to decipher that the first Cotton band is generated by the poly(diphenylacetylene) core and not only by the polyene backbone. The dynamic behavior of poly-(S)-2 is also demonstrated by a helix inversion effect produced by conformational changes at the pendant groups when annealed in solvents with different donor abilities. This phenomenon is accompanied by an inversion of the circular polarized luminescence of the PDPA (CPL switch).

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“…[30][31][32][33][34] Weck et al pioneered using ROMP to prepare supramolecular telechelic polymers. [35][36][37][38][39][40] They successfully prepared supramolecular mono-telechelic polymers via ROMP and synthesized functional Grubbs catalysts that contain different supramolecular motifs. Several of these polymers were further orthogonally assembled into supramolecular block copolymers by non-covalent recognition.…”

Section: Introductionmentioning

confidence: 99%

A Modular and Efficient Synthetic Platform for the Construction of Supramolecular Mono-telechelic Polymers

Liu

Huang

Liu

2022

Preprint

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Supramolecular telechelic polymers are intriguing macromolecular systems for the construction of complex supramolecular systems and responsive soft materials. In this work, we report a practical synthetic approach to preparing supramolecular mono-telechelic polymers with high efficiency and modularity. With a combination of in situ catalyst functionalization, ring- opening metathesis polymerization, and post-polymerization modification, a series of supramolecular mono-telechelic polymers with different supramolecular end-groups and sidechains are synthesized. Several selected examples are then discussed in detail to demonstrate their potential in constructing hierarchical supramolecular architectures, adaptive materials, and supramolecular biomaterials. It is highly anticipated that the synthetic approach reported here will provide rapid and controlled access to complex supramolecular telechelic polymers with tailored functions.

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Secondary Structure in Nonpeptidic Supramolecular Block Copolymers

Cited by 24 publications

References 74 publications

Alkyne-Palladium(II)-Catalyzed Living Polymerization of Isocyanides: An Exploration of Diverse Structures and Functions

Alkyne-Palladium(II)-Catalyzed Living Polymerization of Isocyanides: An Exploration of Diverse Structures and Functions

Dissymmetric Chiral Poly(diphenylacetylene)s: Secondary Structure Elucidation and Dynamic Luminescence

A Modular and Efficient Synthetic Platform for the Construction of Supramolecular Mono-telechelic Polymers

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