One-Step Synthesis of One-Dimensional Supramolecular Assemblies Composed of Helical Macromolecular Building Blocks

Abstract

Living systems achieve sophisticated functions using supramolecular protein assemblies, in which the protein building blocks possess a specific secondary structure and are noncovalently arranged in a preprogrammed manner. Herein, we demonstrate the one-step synthesis of one-dimensional macromolecular assemblies by simply mixing a glycine-based isocyanide with a nickel catalyst, in which helical constituent polymers are linked end-to-end through multiple hydrogen bonds. The applicable scope of this approach is not confined to a particular monomer bearing a specially designed pendant, but covers a wide range of glycine-based isocyanides with or without aromatic and other functional groups. Surprisingly, copolymerization with an analogous chiral isocyanide (1 mol %) afforded an almost perfect one-handed helical supramolecular fiber owing to intramolecular/intermolecular dual chiral amplifications. The simplicity and broad applicability of this approach, which can also afford exquisite chiral amplification, enable the creation of a wide variety of functional supramolecular assemblies and provide access to new supramolecular materials.

Biased Symmetry Breaking and Chiral Control by Self‐Replicating in Achiral Tetradentate Platinum (II) Complexes

“…The Pt‐L 1 12 and Pt‐L 1 16 show intense CD signals in a range of 200–550 nm at the LCs phase, which is consistent with their UV/Vis absorption spectra (Figures 2 a,b; Supporting Information, Figures S16a, S18). As shown in Figure 2 b, there are two main sets of exciton‐coupled CD signals throughout CD spectra, one is at 342 and 376 nm with a zero‐crossing at 355 nm in ligand‐centered charge transitions (LC) absorption range and the other at 400 and 438 nm with a zero‐crossing at 419 nm in metal‐to‐ligand charge transfer (MLCT) transition range, suggesting that the absorbing chromophores are oriented chirally with respect to each other in LCs phase [51–53] . Moreover, the quenched LCs films are used to investigate CD signals at different sites of the sample (see the Supporting Information, Section 5 for details), the same CD spectra were observed except for some variation in absorption intensity when the CD experiments were repeatedly carried out 30 times at different positions of the film (Figure 2 c; Supporting Information, Figure S17), indicating that Pt‐L 1 16 forms an enantiomerically enriched single domain, which suggests that the biased symmetry breaking emerged in LCs phase.…”

Preparation of poly(thiophene-alt-pyrrole) bearing chiral LC group

“…In other words, distance chirality of terminal optically active group in the mesogen induces main chain chirality. In the previous studies, main chain chirality of polymers was induced by chiral side chain located near position to the main chain, showing molecular functionalities [17][18][19][20][21][22][23]. The polymer prepared in this study is first founding in researches of aromatic LC conjugated polymers that the optically active group in the terminal induces main chain chirality from distance in molecular level.…”

Synthesis and Nitrite/Sulfite Electrochemical Response Investigation of Fluorene‐Based, Cross‐Linked Polyisocyanide

“…[10,11] In this process, isocyanide undergoes addition reaction and is converted into imine (─C═N─) group. [12] Current reports regarding PICs mainly focus on the preparation of lineartype PICs (with monofunctional isocyanide monomers as the starting materials), and applications of them in optics, [13,14] chiral catalysis, [15,16] functional gels, [10,17] controlled drug release, [18,19] K. Xu, Prof. W. Shi, K. Zhang, S. Liu, Prof. Z. Xie Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering Southwest Petroleum University Chengdu 610500, China E-mail: shiwei80@swpu.edu.cn; xjuwshi@gmail.com…”

“…[10,11] In this process, isocyanide undergoes addition reaction and is converted into imine (─C═N─) group. [12] Current reports regarding PICs mainly focus on the preparation of lineartype PICs (with monofunctional isocyanide monomers as the starting materials), and applications of them in optics, [13,14] chiral catalysis, [15,16] functional gels, [10,17] controlled drug release, [18,19] DOI: 10.1002/mame.202100173 and so on. As compared to this, the development of cross-linked PICs, which can derive from multifunctional isocyanide starting monomers, has not attracted much attention by far.…”