Exploiting the Mechanical Bond Effect for Enhanced Molecular Recognition and Sensing

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(14)

Published: Jan. 4, 2024

The ubiquity of charged species in biological and industrial processes has resulted ever-increasing interest their selective recognition, detection, environmental remediation. Building on the established coordination chemistry principles chelate macrocyclic effects, host preorganization, supramolecular chemists seek to construct specific 3D binding cavities reminiscent biotic systems enhance host-guest affinity selectivity. Mechanically interlocked molecules (MIMs) present a wholly unique platform for synthetic design, wherein topologies afforded by mechanical bond enable decoration non-covalent interactions with range target guest geometries. Notably, MIM exhibit effect augmented affinities selectivities variety species, compared non-interlocked acyclic macrocycle analogs. Furthermore, modular nature synthesis facilitates incorporation optical electrochemical reporter groups, enabling fabrication highly sensitive molecular sensors. This review discusses development recognition sensing MIMs, from first reports late 20

Language: Английский

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Solution and Solvent‐Free Stopper Exchange Reactions for the Preparation of Pillar[5]arene‐containing [2] and [3]Rotaxanes

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(12)

Published: Jan. 2, 2024

Abstract Diamine reagents have been used to functionalize a [2]rotaxane building block bearing an activated pentafluorophenyl ester stopper. Upon first acylation, intermediate host‐guest complex with terminal amine function is obtained. Dissociation of the occurs in solution and acylation released axle generates elongated subunit. In contrast, corresponding [3]rotaxane can be obtained if reaction conditions are appropriate stabilize inclusion mono‐amine pillar[5]arene. This case when stopper exchange performed under mechanochemical solvent‐free conditions. Alternatively, newly introduced amide group large enough prevent dissociation, second provides exclusively [3]rotaxane. On other hand, detailed conformational analysis has also carried out by variable temperature NMR investigations. A complete understanding shuttling motions pillar[5]arene subunit along axles rotaxanes reported therein achieved help density functional theory calculations.

Language: Английский

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Halogen bonding BODIPY-appended pillar[5]arene for the optical sensing of dicarboxylates and a chemical warfare agent simulant

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A novel halogen bonding pillararene, decorated with BODIPY fluorescent reporter groups, demonstrated strong sensing of environmentally damaging dicarboxylates and a chemical warfare agent simulant in highly competitive aqueous-containing media.

Language: Английский

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Influence of the Nature of Group 15 Element on [Au^I]–C≡E/Azide 1,3-Dipolar Cycloaddition Reaction

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The impact of the nature Group 15 element on both bonding situation and reactivity gold(I)-C ≡ E (E = N to Bi) complexes has been studied quantum chemically within density theory functional framework. For this purpose, 1,3-dipolar cycloaddition reaction involving tBuN3 as dipole selected its main features, including regioselectivity transformation in-plane aromaticity corresponding transition structures, have investigated. It is found that increased one moves down (N ≪ P < As Sb Bi). This trend rationalized by using combined activation strain model energy decomposition analysis methods, which indicate process mainly dominated required reactants reach state geometries.

Language: Английский

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An Inorganic Click Reaction for the Synthesis of Interlocked Molecules

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: July 14, 2023

We describe the use of cyaphide-azide 1,3-dipolar cycloaddition reaction for synthesis a new class inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an click reaction. These transformations proceed good yields (ca. 65 %) and absence catalyst. The resulting organometallic are air- moisture-stable can be purified by column chromatography under aerobic conditions. targeted were characterized multi-element nuclear magnetic resonance (NMR) spectroscopy, mass-spectrometry, single-crystal X-ray diffraction.

Language: Английский

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Metal Influence on Cyaphide‐Azide 1,3‐Dipolar Cycloaddition Reactions: Aromaticity and Activation Strain

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(15)

Published: Jan. 15, 2024

The factors governing 1,3-dipolar cycloaddition reactions involving C≡P-containing compounds are computationally explored in detail using quantum chemical tools. To this end, the parent process tBuN

Language: Английский

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1,3-Dipolar cyclisation reactions of nitriles with sterically encumbered cyclic triphosphanes: synthesis and electronic structure of phosphorus-rich heterocycles with tunable colour

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 12006 - 12016

Published: Jan. 1, 2024

The acid-mediated cyclisation of sterically encumbered cyclic triphosphanes with nitriles provides access to five-membered cationic and neutral P 3 CN heterocycles tuneable colour.

Language: Английский

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