Metal‐Organic Frameworks and Metal‐Organic Cages – A Perspective

Pilgrim, Ben S.; Champness, Neil R.

doi:10.1002/cplu.202000408

Cited by 75 publications

(60 citation statements)

References 187 publications

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“…Cages are commonly synthesised from a bottom-up building block approach and can be formed from purely organic building blocks 50 or building blocks that contain metal complexes. 51,52 They are candidate materials for solid-state and solution-phase applications in, for example, storage, separations and catalysis. 50,53 Of particular interest is the modularity of their design process, where specific structures or properties are targeted by choice of its constituent building blocks.…”

Section: Molecular Cagesmentioning

confidence: 99%

Stk: An Extendable Python Framework for Automated Molecular and Supramolecular Structure Assembly and Discovery

Turcani¹,

Tarzia²,

Szczypiński³

et al. 2021

Preprint

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<div>Computational software workflows are emerging as all-in-one solutions to speed up the discovery of new materials.</div><div>Many computational approaches require the generation of realistic structural models for property prediction and candidate screening. However, molecular and supramolecular materials represent classes of materials with many potential applications for which there is no go-to database of existing structures or general protocol for generating structures. Here, we report a new version of the supramolecular toolkit, <i>stk</i>, an open-source, extendable and modular Python framework for general structure generation of (supra)molecular structures. Our construction approach follows a bottom-up process and minimises the input required from the user, making <i>stk</i> user-friendly and applicable to many material classes. This version of <i>stk</i> includes metal-containing structures and rotaxanes as well as general implementation and interface improvements. Additionally, this version includes built-in tools for exploring chemical space with an evolutionary algorithm and tools for database generation and visualisation. The latest version of <i>stk</i> is freely available at github.com/lukasturcani/stk</div>

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Section: Molecular Cagesmentioning

confidence: 99%

Stk: An Extendable Python Framework for Automated Molecular and Supramolecular Structure Assembly and Discovery

Turcani¹,

Tarzia²,

Szczypiński³

et al. 2021

Preprint

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“…Metal-organic cages (MOCs) are self-assembled structures derived from carefully selected combinations of metal ions and ligands ( Cook and Stang, 2015 ; Debata et al, 2019 ; Pilgrim and Champness, 2020 ). Porous MOCs of myriad shape and size are capable of binding guest molecules in their cavities ( Rizzuto et al, 2019 ), leading to applications in catalysis ( Yoshizawa et al, 2009 ; Sinha and Mukherjee, 2018 ), storage of reactive species ( Galan and Ballester, 2016 ), molecular separations ( Zhang et al, 2021 ), and drug delivery ( Casini et al, 2017 ) amongst others.…”

Section: Introductionmentioning

confidence: 99%

Structural Flexibility in Metal-Organic Cages

Díaz

Lewis

2021

Front. Chem.

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Metal-organic cages (MOCs) have emerged as a diverse class of molecular hosts with potential utility across a vast spectrum of applications. With advances in single-crystal X-ray diffraction and economic methods of computational structure optimisation, cavity sizes can be readily determined. In combination with a chemist’s intuition, educated guesses about the likelihood of particular guests being bound within these porous structures can be made. Whilst practically very useful, simple rules-of-thumb, such as Rebek’s 55% rule, fail to take into account structural flexibility inherent to MOCs that can allow hosts to significantly adapt their internal cavity. An often unappreciated facet of MOC structures is that, even though relatively rigid building blocks may be employed, conformational freedom can enable large structural changes. If it could be exploited, this flexibility might lead to behavior analogous to the induced-fit of substrates within the active sites of enzymes. To this end, in-roads have already been made to prepare MOCs incorporating ligands with large degrees of conformational freedom. Whilst this may make the constitution of MOCs harder to predict, it has the potential to lead to highly sophisticated and functional synthetic hosts.

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“…This progress has already led to numerous applications (see an extensive survey in reference [5]) and to the preparation of a number of fascinating architectures like, for example, an enantiopure "Russian doll" [6], a triple-stranded mesocate [7], and a cage compound that can be transformed into the covalent organic framework [8]. In the process of the characterization of supramolecular structures, techniques of the liquid state NMR of protons ( 1 H NMR) are crucial, which were most recently outlined in reference [9]. The proton NMR chemical shift in solution is usually the most important 1 H NMR parameter because its value for the investigated hydrogen(s) in a guest molecule generally differs between encapsulated and bulk states, allowing a straightforward analysis of the guest binding and exchange [10].…”

Section: Introductionmentioning

confidence: 99%

A Volumetric Analysis of the 1H NMR Chemical Shielding in Supramolecular Systems

Czernek

Brus

2021

IJMS

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The liquid state NMR chemical shift of protons is a parameter frequently used to characterize host–guest complexes. Its theoretical counterpart, that is, the 1H NMR chemical shielding affected by the solvent (1H CS), may provide important insights into spatial arrangements of supramolecular systems, and it can also be reliably obtained for challenging cases of an aggregation of aromatic and antiaromatic molecules in solution. This computational analysis is performed for the complex of coronene and an antiaromatic model compound in acetonitrile by employing the GIAO-B3LYP-PCM approach combined with a saturated basis set. Predicted 1H CS values are used to generate volumetric data, whose properties are thoroughly investigated. The 1H CS isosurface, corresponding to a value of the proton chemical shift taken from a previous experimental study, is described. The presence of the 1H CS isosurface should be taken into account in deriving structural information about supramolecular hosts and their encapsulation of small molecules.

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Metal‐Organic Frameworks and Metal‐Organic Cages – A Perspective

Cited by 75 publications

References 187 publications

Stk: An Extendable Python Framework for Automated Molecular and Supramolecular Structure Assembly and Discovery

Stk: An Extendable Python Framework for Automated Molecular and Supramolecular Structure Assembly and Discovery

Structural Flexibility in Metal-Organic Cages

A Volumetric Analysis of the 1H NMR Chemical Shielding in Supramolecular Systems

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