Directional Shuttling of a Stimuli‐Responsive Cone‐Like Macrocycle on a Single‐State Symmetric Dumbbell Axle

Cui, Jieshun; Ba, Qiankai; Ke, Hua Zhu; Valkonen, Arto; Jiang, Wei

doi:10.1002/ange.201803349

Cited by 25 publications

(12 citation statements)

References 62 publications

(9 reference statements)

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“…Amine naphthotubes 6 are responsive to acid/base. 26 Their binding properties in the neutral state are similar to the binding properties of 3 and 4, and the syn-configurational isomer 6a can bind organic cation 17 2+ (Figure 7a) with K a = 7.4 × 10 3 M −1 as determined by isothermal titration calorimetry (ITC) in a 1:1 mixture of 1,2-dichloroethane and CH 3 CN at 25 °C. The amine groups of 6a can be protonated and deprotonated through the addition of acid or base.…”

Section: Molecular Recognitionmentioning

confidence: 74%

Naphthotubes: Macrocyclic Hosts with a Biomimetic Cavity Feature

et al. 2019

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CONSPECTUS: Macrocyclic hosts are the principal tools used in supramolecular chemistry because they can recognize other small molecules through non-covalent interactions. However, in terms of recognition ability, known macrocyclic hosts are often not comparable to bioreceptors. This may be due to the lack of functional groups inside the deep cavity, which is a common feature of bioreceptors. Most of the known macrocyclic hosts contain either a hydrophobic cavity or polar binding sites only. Macrocyclic hosts with functional groups inside a hydrophobic cavity are rare. In 2004, Glass and co-workers reported a pair of water-soluble naphthalene-based molecular tubes with amide protons in the well-defined deep cavity. The cavity feature is very similar to that of bioreceptors. However, the amide protons were not used in molecular recognition and were replaced in 2012 with allyl groups in order to improve the hydrophobic effect. We started our work on the basis of the Glass molecular tubes but paid close attention to the functional groups in the deep cavity. In this Account, we summarize our results on these biomimetic receptors, which we call naphthotubes. The inward-directed functional groups endow the corresponding naphthotubes with unique recognition abilities. Naphthotubes with hydrogen-bond acceptors (ether, ester, and imine) prefer to bind organic cations; naphthotubes with hydrogen-bond donors (urea, thiourea, and amide) can bind neutral molecules; amine naphthotubes are stimuli-responsive to acid/base. In particular, the water-soluble amide naphthotubes are able to selectively recognize highly hydrophilic molecules in watera generally accepted challenge in supramolecular chemistry. The unique recognition ability of these naphthotubes provides the basis for their applications in sensing, self-assembly, and molecular machines. Fluorescent sensing of environmental contaminants in water, chiroptical sensing of small chiral molecules, allosteric cooperative self-assembly, dissipative selfassembly, and directional molecular shuttles have been demonstrated with these naphthotubes. Overall, we hope to convey the message that these naphthotubes have unique recognition properties and promising applications in diverse fields. We believe that further exploration of this class of macrocycles may lead to practical applications in, for example, biomedical science, environmental science, and other related fields.

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Section: Molecular Recognitionmentioning

confidence: 74%

Naphthotubes: Macrocyclic Hosts with a Biomimetic Cavity Feature

et al. 2019

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“… 1 − 3 A key ambition of supramolecular chemists is to engineer molecular machines capable of performing useful work, such as catalysis, transport, and host–guest binding, with comparable precision. 4 , 5 To date, synthetic molecular machines have featured complex arrangements of moving parts, including rings that shuttle between stations on a linear or circular track 6 , 7 and crane-like arms that can transfer labile moieties between reactive docking sites. 8 , 9 …”

Section: Introductionmentioning

confidence: 99%

High-Yielding Flow Synthesis of a Macrocyclic Molecular Hinge

et al. 2021

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Many molecular machines are built from modular components with well-defined motile capabilities, such as axles and wheels. Hinges are particularly useful, as they provide the minimum flexibility needed for a simple and pronounced conformational change. Compounds with multiple stable conformers are common, but molecular hinges almost exclusively operate via dihedral rotations rather than truly hinge-like clamping mechanisms. An ideal molecular hinge would better reproduce the behavior of hinged devices, such as gates and tweezers, while remaining soluble, scalable, and synthetically versatile. Herein, we describe two isomeric macrocycles with clamp-like open and closed geometries, which crystallize as separate polymorphs but interconvert freely in solution. An unusual one-pot addition cyclization reaction was used to produce the macrocycles on a multigram scale from inexpensive reagents, without supramolecular templating or high-dilution conditions. Using mechanistic information from NMR kinetic studies and at-line mass spectrometry, we developed a semicontinuous flow synthesis with maximum conversions of 85–93% and over 80% selectivity for a single isomer. The macrocycles feature voids that are sterically protected from guests, including reactive species such as fluoride ions, and could therefore serve as chemically inert hinges for adaptive supramolecular receptors and flexible porous materials.

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“…During the last six years, we reported a series of naphthol‐ based macrocyclic receptors which have been used in molecular recognition, molecular sensing, molecular machine, cooperative self‐assembly and supramolecular hydrogel . We recently synthesized a tetralactam macrocycle with 2,3‐dibutoxylnaphthalene .…”

Section: Background and Originality Contentmentioning

confidence: 99%

Selective Recognition of Phenazine by 2,6‐Dibutoxylnaphthalene‐Based Tetralactam Macrocycle

Wang

Valkonen

et al. 2019

Chin. J. Chem.

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Summary of main observation and conclusion A 2,6‐dibutoxylnaphthalene‐based tetralactam macrocycle was designed and synthesized. This macrocycle shows highly selective recognition to phenazine – a well‐known secondary metabolite in bacteria and an emerging disinfection byproduct in drinking water. In contrast, the macrocycle shows no binding to the structurally similar dibenzo‐1,4‐dioxin. It was revealed that hydrogen bonding, π‐π and σ‐π interactions are the major driving forces between phenazine and the new tetralactam macrocycle. A perfect complementarity in electrostatic potential surfaces may explain the high selectivity. In addition, the macrocycle shows fluorescent response to phenazine, demonstrating its potential in fluorescent detection of phenazine.

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Directional Shuttling of a Stimuli‐Responsive Cone‐Like Macrocycle on a Single‐State Symmetric Dumbbell Axle

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 25 publications

References 62 publications

Naphthotubes: Macrocyclic Hosts with a Biomimetic Cavity Feature

Naphthotubes: Macrocyclic Hosts with a Biomimetic Cavity Feature

High-Yielding Flow Synthesis of a Macrocyclic Molecular Hinge

Selective Recognition of Phenazine by 2,6‐Dibutoxylnaphthalene‐Based Tetralactam Macrocycle

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