Supramolecular dimers are elementary units allowing the build-up of multi-molecule architectures. New among these are cyanostar-stabilized dimers of phosphate and phosphonate anions. While the anion dimerization at the heart of these assemblies is reliable, the covalent synthesis leading to this class of designer anions serves as a bottleneck in the pathway to supramolecular assemblies. Herein, we demonstrate the reliable synthesis of 14 diverse anionic monomers by Heck coupling between vinyl phosphonic acid and aryl bromide compounds. When this synthesis is combined with reliable anion dimerization, we show formation of supramolecular dimers and polymers by co-assembly with cyanostar macrocycles. The removal of the covalent bottleneck opened up a seamless synthetic route to iterate through three monomers affording the solubility needed to characterize the mechanism of supramolecular polymerization. We also test the idea that the small size of these vinyl phosphonates provide identical dimer stabilities across the library by showing how mixtures of anions undergo statistical (social) self-sorting. We exploit this property by preparing soluble copolymers from the mixing of different monomers. This multi-anion assembly shows the utility of a library for programming properties.
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Helical Chirality of Supramolecular Columns and Spheres Self‐Organizes Complex Liquid Crystals, Crystals, and Quasicrystals
Homochiral helical self‐organizations provide some of the most fundamental architectures of biological macromolecules and of their co‐assemblies although they were first discovered and elucidated only during the early 1950. Helical synthetic covalent macromolecules started to be discovered soon after and were followed by supramolecular macromolecules and their co‐assemblies few decades later. This perspective will provide a brief historical development of chiral helical self‐organizations in biology and in supramolecular chemistry. Helical covalent and supramolecular macromolecules self‐organize and co‐organize helical supramolecular columns and spherical helices that can generate complex liquid crystals, crystals including Frank‐Kasper phases, and quasicrystals. The design of new functions based on synthetic helical assemblies will also be discussed. Personal events from the life of scientists contributing to these developments are also briefly mentioned.
more » « less- PAR ID:
- 10307633
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Israel Journal of Chemistry
- Volume:
- 61
- Issue:
- 9-10
- ISSN:
- 0021-2148
- Format(s):
- Medium: X Size: p. 530-556
- Size(s):
- p. 530-556
- Sponsoring Org:
- National Science Foundation
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