Mimicking the structure of proteins using synthetic polymers requires building blocks with structural similarity and the use of various noncovalent and dynamic covalent interactions. We report the synthesis of helical poly(isocyanide)s bearing diaminopyridine and pyridine side-chains and the multistep functionalization of the polymers' side-chains using hydrogen bonding and metal coordination. The orthogonality of the hydrogen bonding and metal coordination was proved by varying the sequence of the multistep assembly. The two side-chain functionalizations are reversible through the use of competitive solvents and/or competing ligands. Throughout the assembly and disassembly, the helical conformation of the polymer backbone is sustained as proved by circular dichroism spectroscopy. These results open the possibility to incorporate helical domains into complex polymer architectures and create a helical scaffold for smart materials.
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http://dx.doi.org/10.1021/acs.macromol.2c02224 | DOI Listing |
Chem Sci
August 2024
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun Jilin 130012 China.
Porous materials have attracted interest due to their high specific surface area and rich functionality. Immobilizing organocatalysts onto porous polymers not only boosts enantioselectivity but also improves the reaction rates. In this work, a series of porous polymers C-poly-3s with rigid polyisocyanide-carrying secondary amine pendants as building blocks were successfully prepared.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
Porous frameworks with controlled pore structure and tunable aperture are greatly demanded. However, precise synthesis of this kind of materials is a formidable challenge. Herein, we report the fabrication of two-dimensional (2D) supramolecular polymer frameworks using a precisely synthesized rod-like helical polyisocyanide as link.
View Article and Find Full Text PDFAnal Chem
December 2023
State Key Laboratory of Applied Organic Chemistry, Lanzhou Magnetic Resonance Center, College of Chemistry and Chemi-cal Engineering, Lanzhou University, Lanzhou 730000, China.
The development of chiral alignment media for measuring anisotropic NMR parameters provides an opportunity to determine the absolute configuration of chiral molecules without the need for derivatization. However, chiral alignment media with a high and robust enantiodiscriminating property for a wide range of chiral molecules are still scarce. In this study, we synthesized cholesterol-end-functionalized helical polyisocyanides from a chiral monomer using a cholesterol-based alkyne-Pd(II) initiator.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2023
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China.
A pair of enantiomeric photoswitchable Pd catalysts, alkyne-Pd /L and alkyne-Pd /L , were prepared via the coordination of alkyne-Pd and azobenzene-modified phosphine ligands L and L . Owing to the cis-trans photoisomerization of the azobenzene moiety, alkyne-Pd /L and alkyne-Pd /L exhibited different polymerization activities, helix-sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A-1 could be polymerized efficiently using alkyne-Pd /L under dark condition in a living/controlled manner.
View Article and Find Full Text PDFNat Commun
November 2023
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China.
Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is greatly desired. In this work, a family of amphiphilic one-handed helical polyisocyanides bearing phosphine pendants is prepared, which self-assembles into well-defined chiral micelles in water and showed thermo-responsiveness with a cloud point of approximately 38.4 °C.
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