Stoichiometry-Controlled Chirality Induced by Co-assembly of Tetraphenylethylene Derivative, γ-CD, and Water-Soluble Pillar[5]arene

Abstract

A stoichiometry-controlled chirality induction was successfully achieved through coassemblies of amphiphilic tetraphenylethylene derivative TPEA, γ-cyclodextrin (γ-CD), and water-soluble pillar[5]arene WP5 in aqueous solution. Stoichiometric variation of WP5 was found to be an effective strategy to induce topological transition between the pseudo[4]rotaxane and the vesicular form. Interestingly, the formation of pseudo[4]rotaxane triggered dual chirality induction from chiral γ-CD to TPEA (negative ICD 1 ), and then, to dynamically racemic WP5 (positive ICD 2 ), whereas both ICD 1 and ICD 2 were silent in the vesicular form.

Multicharged cyclodextrin supramolecular assemblies

“…46). 378 The tetraphenylethylene unit of TPEA could be encapsulated into the chiral cavity of g-CD through hydrophobic interactions and lead to obvious negative induced circular dichroism (ICD 1 ). During the addition of WP5 (0.05-0.20 equiv.)…”

Redox-Driven Chiral Inversion of Water-Soluble Pillar[5]arene with l-Cystine Derivative in the Aqueous Medium

“…Since the first report of pillararenes and derivatives, , they have been extensively developed in various areas over the past several years. − Typically, pillararenes have an interesting and unique planar chirality, which is dynamically reversible between the p R and p S conformations at room temperature. , Interestingly, the planar chirality of pillararenes could be induced and switched by the construction of pseudo[1]­catenanes based on the redox property of the ferrocene moiety or by the addition of an achiral guest or solvents, a metal cation, or an acid/base or controlled by temperature . Additionally, there are some other approaches to induce the planar chirality of pillararenes by forming a chiral (pseudo)­rotaxane, , adding chiral α-amino esters or acids, − or forming the regulator-assisted chiral memory of pillararenes with a chiral inducer . Recently, we found that the different planar chiralities of the water-soluble pillar[5]­arene WP5 could be induced by a binding ester moiety or a side-chain moiety of α-amino acids esters in water .…”

Cyclodextrin-pillar[n]arene hybridized macrocyclic systems

“…Except for using CD as the external stimulus to control the pillar[ n ]arene-based supramolecular self-assembly, pillar[ n ]arene could also be employed to tune the CD-based supramolecular architectures reversibly. 56 For example, abacus-like pseudo[4]rotaxane ( pR -Na + · H1 ) 2 ⊃ G8 ⊂γ-CD (Fig. 3) could be synthesized by using the linear guest molecule—amphiphilic tetraphenylethylene derivative ( G8 , Scheme 3) as the “rod” 75,76 to attract both γ-CD and Na + · H1 as the “wheel” (Scheme 3) in a specialized stoichiometry, i.e.…”