Controlling supramolecular polymerization through multicomponent self‐assembly

Abstract

The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

Diketopyrrolopyrrole Columnar Liquid‐Crystalline Assembly Directed by Quadruple Hydrogen Bonds

“…[1][2][3][4][5][6][7][8] This is commonly performed by encoding information in the molecular building blocks to control their assembly process and packing arrangement which, in turn, define the properties.I nt his regard, among non-covalent interactions particularly hydrogen bonds (H-bonds) evolved as most useful for the creation of functional non-covalent architectures,such as supramolecular polymers, [9][10][11][12] gels, [13] and liquid crystals. [1][2][3][4][5][6][7][8] This is commonly performed by encoding information in the molecular building blocks to control their assembly process and packing arrangement which, in turn, define the properties.I nt his regard, among non-covalent interactions particularly hydrogen bonds (H-bonds) evolved as most useful for the creation of functional non-covalent architectures,such as supramolecular polymers, [9][10][11][12] gels, [13] and liquid crystals.…”

Reversible Loading of Nanoscale Elements on a Multicomponent Supramolecular Polymer System by Using DNA Strand Displacement

“…[1][2][3][4][5][6][7][8][9] These features make supramolecular polymer materials excellent candidates for the construction of modular multicomponent systems, in which functional monomers can be introduced by simply matching the noncovalent interactions of the native and functional monomer units. [10][11][12] Engineering of functionw ithin shape-persistent, one-dimensional supramolecular polymers consisting of amphiphiles can involvet ethering [13][14][15][16][17] or embedding [18][19][20][21] of specific (bio)molecular or nanoscale components. For example, bioactive peptides [12,14,22] and drugs [16,23] have been incorporated into them through the use of various covalentc hemistries to prepare monomers that self-assemble into supramolecular polymers with am ultivalent presentation of ag iven component for applications in the biomedical area.…”

Photomodulation of DNA‐Templated Supramolecular Assemblies

“…Fine control over the formation of supramolecular assemblies and polymers through DNA templating to achieve functional nanostructures, with possible applications in sequence‐controlled polymers, (bio)sensing, and delivery, has recently gained great interest . In this regard, achieving DNA‐templated multicomponent assemblies for which the organisation and function can be modulated upon external stimuli is a fascinating challenge ,. Among the different stimuli, light is a practical trigger for enabling responsive materials, as exemplified by the incorporation of photoswitchable ligands into biomolecular systems in view of controlling their conformation and activity in a reversible manner .…”