Alkali Metal Halide Ion‐Pair Binding in Conformationally Dynamic Halogen Bonding Heteroditopic [2]Rotaxanes

Tay, Hui Min; Docker, Andrew; Tse, Yuen Cheong; Beer, Paul D.

doi:10.1002/chem.202301316

Cited by 10 publications

(1 citation statement)

References 46 publications

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“…It was found that these systems selectively bind LiCl over LiBr or LiI. Follow-up studies were reported to extend the applicability of the approach to other alkali metal halides [98,99]. It is hoped that the DFT computational results presented in this work provide a foundation and motivation to help expand research in the field of halogen bonds.…”

Section: Future Perspectivesmentioning

confidence: 78%

A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study

Parra

2023

Inorganics

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The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C4h symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li+ at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li+ is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li+ complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li+. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li+ binding abilities.

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Section: Future Perspectivesmentioning

confidence: 78%

A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study

Parra

2023

Inorganics

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Exploiting the Mechanical Bond Effect for Enhanced Molecular Recognition and Sensing

Wilmore,

Beer

2024

Advanced Materials

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The ubiquity of charged species in biological and industrial processes has resulted in ever‐increasing interest in their selective recognition, detection and environmental remediation. Building on the established coordination chemistry principles of the chelate and macrocyclic effects, and host preorganization, supramolecular chemists seek to construct specific three‐dimensional binding cavities reminiscent of biotic systems to enhance host‐guest binding affinity and selectivity. Mechanically interlocked molecules (MIMs) present a wholly unique platform for synthetic host design, wherein topologies afforded by the mechanical bond enable the decoration of three‐dimensional cavities for non‐covalent interactions with a range of target guest geometries. Notably, MIM host systems exhibit mechanical bond effect augmented affinities and selectivities for a variety of charged guest species, compared to non‐interlocked acyclic and macrocycle host analogues. Furthermore, the modular nature of MIM synthesis facilitates incorporation of optical and electrochemical reporter groups, enabling fabrication of highly sensitive and specific molecular sensors. This review discusses the development of recognition and sensing MIMs, from the first reports in the late 20th century through to the present day, delineating how their topologically preorganized and dynamic host cavities enhance charged guest recognition and sensing, demonstrating the mechanical bond effect as a potent tool in future chemosensing materials.This article is protected by copyright. All rights reserved

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Synthesis of ‘Impossible’ Rotaxanes

Saura‐Sanmartin

2024

Chemistry A European J

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'Impossible' rotaxanes, which are constituted by interlocked components without obvious binding motifs, have attracted the interest of the mechanically interlocked molecules (MIMs) community. Within the synthetic efforts reported in the last decades towards the preparation of MIMs, some innovative protocols for accessing 'impossible' rotaxanes have been developed. This short review highlights different selected synthetic examples of 'impossible' rotaxanes, as well as suggests some future directions of this research area.

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Alkali Metal Halide Ion‐Pair Binding in Conformationally Dynamic Halogen Bonding Heteroditopic [2]Rotaxanes

Cited by 10 publications

References 46 publications

A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study

A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study

Exploiting the Mechanical Bond Effect for Enhanced Molecular Recognition and Sensing

Synthesis of ‘Impossible’ Rotaxanes

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