Control of the Assembly of a Cyclic Hetero[4]pseudorotaxane from a Self-complementary [2]rotaxane

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 Apr 17

PMID 37063802

Authors

Adrian Saura-Sanmartin

Tomas Nicolas-Garcia

Aurelia Pastor

David Quinonero

Mateo Alajarin

Alberto Martinez-Cuezva

Jose Berna

Affiliations

Soon will be listed here.

Abstract

The synthesis of a ditopic interlocked building-block and its self-assembly into a cyclic dimer is reported herein. Starting from a thread with two recognition sites, a three-component clipping reaction was carried out to construct a bistable [2]rotaxane. A subsequent Suzuki cross-coupling reaction allowed the connection of a second ring to that of the rotaxane, affording a self-complementary ditopic system. NMR studies were carried out to identify a cyclic hetero[4]pseudorotaxane as the main supramolecular structure in solution. Its assembly is the result of a positive cooperativity operating in the hydrogen-bonding-driven assembly of this mechanically interlocked supramolecule, as revealed by computational studies. The increase of the polarity of the solvent allows the disruption of the intercomponent interactions and the disassembly of the hetero[4]pseudorotaxane into the two interlocked units. The disassembly of the cyclic dimer was also achieved through a Diels-Alder reaction over the fumaramide binding site of the thread, triggering the translational motion of the entwined macrocycle to an adjacent glycylglycine-based station and precluding the supramolecular dimerization. The competitive molecular recognition of a guest molecule by one of the self-templating counterparts of the dimer also led to the controlled disassembly of the hetero[4]pseudorotaxane.

Citing Articles

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Light-responsive rotaxane-based materials: inducing motion in the solid state.

Saura-Sanmartin A Beilstein J Org Chem. 2023; 19:873-880.

PMID: 37346498 PMC: 10280056. DOI: 10.3762/bjoc.19.64.

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