Integrative Self‐Sorting in a Three Component System Leading to Formation of Long Fibrous Structures

Abstract

In this paper we report the integrative self‐sorting processes in a three‐component system consisting of β‐CD, a bis‐adamantane derivative AD‐AD and a bis‐pyromellitic diimide derivative PI‐PI in a 2:1:1 ratio, leading to the slow evolution of long fibers. Using TEM, AFM and time‐dependent ICD measurements of the three‐component system and the constituent two‐component systems (β‐CD/AD‐AD and β‐CD/PI‐PI), involvement of two social self‐sorting and two narcissistic self‐sorting processes, which led to the evolution of the long fibers, were identified. Initially a bis‐inclusion complex of β‐CD and AD‐AD is formed through a social self‐sorting process. The bis‐inclusion complex undergoes a narcissistic self‐assembly to give vesicles. The key step in the integrative self‐sorting is binding of PI‐PI to the vesicle surface through rim‐binding association. The rim‐binding motif is effectively exploited herein to perform the functions of vesicle recognition, and vesicle joining.

Self-Assembly and Photochemistry of a Pyrene-Methyl Viologen Supramolecular Fiber System

“…49 Joining of vesicles to give fibers is also reported. 46,53,54 The formation of vesicles and fibers from the dendritic inclusion complex can be thus explained. However, close packing of PY over PY and β-CD over β-CD may not occur in such vesicles and the severe dampening observed for the 1 H NMR signals of PY cannot be explained in this way.…”

Supramolecular copolymerization through self-correction of non-polymerizable transient intermediates

“…Self-sorting is an exquisite strategy to construct sequence-controlled supramolecular copolymers. 26,[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] The successful construction of such systems follows a simple thermodynamic rule which requires a large difference in binding constants among interaction pairs. However, the detailed self-sorting pathways, and the evolution of possible transient intermediates are relatively unexplored and thereby are still elusive.…”

Self-Assembly of a β-Cyclodextrin Bis-Inclusion Complex into a Highly Crystalline Fiber Network. An Effective Strategy for Null Aggregate Design

“…For example, bolaamphiphiles are known to self-assemble into spheres, − gels, ,− discs, − vesicles, − helical structures, − tubes − and so forth. Construction of supramolecular amphiphiles and study of their self-assembly into various morphological structures is an important aspect of current supramolecular chemistry. ,− Bis-inclusion complexes of cyclodextrins (CD), where the included moieties are present at the two ends of a sufficiently hydrophobic linker unit, can be considered as supramolecular bolaamphiphiles. ,,− The high water solubility of CDs makes both ends of these bis-inclusion complexes hydrophilic. Although supramolecular amphiphiles are known to self-assemble into various types of morphologies, bis-inclusion complexes of CDs are known to self-assemble only into vesicles. − In this paper, we present self-assembly of a β-CD bis-inclusion complex into crystalline fibers for the first time.…”