Control over differentiation of a metastable supramolecular assembly in one and two dimensions

Abstract

Molecular self-assembly under kinetic control is expected to yield nanostructures that are inaccessible through the spontaneous thermodynamic process. Moreover, time-dependent evolution, which is reminiscent of biomolecular systems, may occur under such out-of-equilibrium conditions, allowing the synthesis of supramolecular assemblies with enhanced complexities. Here we report on the capacity of a metastable porphyrin supramolecular assembly to differentiate into nanofibre and nanosheet structures. Mechanistic studies of the relationship between the molecular design and pathway complexity in the self-assembly unveiled the energy landscape that governs the unique kinetic behaviour. Based on this understanding, we could control the differentiation phenomena and achieve both one- and two-dimensional living supramolecular polymerization using an identical monomer. Furthermore, we found that the obtained nanostructures are electronically distinct, which illustrates the pathway-dependent material properties.

Supramolecular Copolymers: Structure and Composition Revealed by Theoretical Modeling

“…13−15 Exciting examples are found in kinetically controlled living copolymerizations as developed for covalent block copolymers 11e−11h and small molecules, 13c−13g which show that kinetically trapped block structures can be formed in supramolecular copolymers. For systems under thermodynamic equilibrium, a combined experimental and theoretical approach proved to be a robust method to unravel several issues, although these endeavors were typically limited to one-component or simple two-component systems.…”

Tunable Supramolecular Assembly and Photoswitchable Conversion of Cyclodextrin/Diphenylalanine‐Based 1D and 2D Nanostructures

“…Kim et al reported ao ne-cycle zero-dimensional/one-dimensional conversion of pyrenemodified dendritic self-assembly between vesicles and nanotubes induced by the sequential addition of cyclodextrin (CD) and poly(propylene glycol). [11] Herein, we report ap hotocontrolled, reversible,a nd repeatable nanotube-nanosheet, that is,o ne-dimensional/twodimensional, morphological conversion of the supramolecular assembly of adamantanyl-modified diphenylalanine (Ada-FF)w ith azobenzene-bridged bis(b-CD) (H; Scheme 1). [10] More recently,T akeuchi and Sugiyasu et al achieved one-and two-dimensional supramolecular assemblies (nanofibers/nanosheets)v ia control of the kinetic self-assembly process of ametastable porphyrin.…”

Self-Assembly of Bodipy-Derived Extended π-Systems

“…So far, the growth of supramolecular polymers is considered to be one-dimensional (1D) in nature, however, recently, two-dimensional (2D) growth by seeded supramolecular polymerization approach has been realized. 14,15 Therefore, understanding the pathway complexity and the mechanistic details of supramolecular polymerization has created great opportunities for researchers to design functional supramolecular assemblies similar to that of several biological systems. 1620 Porphyrin, squaraine, Bodipy, rylene and cyanine dyes, etc.…”