Cation-Directed Self-Assembly of Macrocyclic Diacetylene for Developing Chromogenic Polydiacetylene

Abstract

The cation-directed self-assembly process has emerged as a fascinating approach for constructing supramolecular architectures and manifested a diverse range of assembly related applications. Herein, we synthesized a macrocyclic structure containing bis-amidopyridine and photopolymerizable diacetylene template, PyMCDA. Owing to the metal coordination affinity of bis-amidopyridine and the π−π stacking characteristic of diacetylene template and complementary to the cyclic molecular framework, Cs + -directed organic nanotubes are generated via unidirectional selfassembly of PyMCDA. The monomeric PyMCDA nanotubes are transformed into the covalently cross-linked chromogenic polydiacetylene nanotubes (PyMCPDA-Cs + ) by UV-promoted topochemical polymerization. The result of a metal−ligand coordination characteristic, geometric parameters in solid-state assemblies, and topochemical polymerization behavior reveals a generation of Cs + ion inserted nanotubes. Interestingly, PyMCDA-Cs + nanotubes display thermochromic property with a brilliant blue-to-red color transition.

Self‐Assembly Behavior of Diacetylenic Acid Molecules upon Vapor Deposition: Odd–Even Effect on the Film Morphology

“…[17,18] Tremendouse fforts have been made towards aligning diacetylene molecules into hierarchical nanostructurest hrough various techniques involvingn on-covalent forces. [19][20][21] Nevertheless, limited successh as been achieved, presumably owing to the strict packingr equirements of topochemical polymerization and the numerous defects that may evolve during the preparation and polymerization processes. [22] Ab etter understanding and improvedc ontrol of the self-assembling behaviors for diacetylene molecules are needed.…”

“…Pre‐organizing diacetylenic monomers directionally and then subjecting them to topochemical polymerization to form aligned conjugated polymers are highly interesting [17, 18] . Tremendous efforts have been made towards aligning diacetylene molecules into hierarchical nanostructures through various techniques involving non‐covalent forces [19–21] . Nevertheless, limited success has been achieved, presumably owing to the strict packing requirements of topochemical polymerization and the numerous defects that may evolve during the preparation and polymerization processes [22] .…”

Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

“…Cyclic monomers containing multiple diacetylene units (macrocyclic diacetylenes, MCDA) are established as excellent precursors for the topochemical synthesis of PDA-based organic tubular polymers that possess nanometre-sized interior cavities. 2 d ,27 Suitably functionalized MCDAs containing multiple DA units self-stack into a columnar assembly through non-covalent interactions, 28 sometimes aided by templates, 29 forming a supramolecular nanotube. The subsequent 1,4-addition polymerization of the DA units along the columns results in nanotubular polymers, bearing PDA side-walls.…”

Synthesis of a Trimeric Macrocyclic Diacetylene

“…Interestingly, self-assemblies of macrocycles containing diacetylene moieties should have columnar structures, which upon polymerization would generate PDAs having rigid, carbon nanotube (CNT)-like structures. [16][17][18][19][20][21][22][23] In an effort to further explore this fascinating feature of PDAs, we designed and synthesized several functional macrocyclic diacetylenes (MCDAs) and demonstrated that they undergo columnar packing and UV-induced polymerization to produce tubular PDAs. [20][21][22][23] Thus far, studies carried out in this area have only focused on PDA nanotubes that are generated from assemblies of single MCDA components.…”