A Combined Experimental and Computational Exploration of Heteroleptic cis‐Pd2L2L’2 Coordination Cages through Geometric Complementarity DOI Creative Commons
Andrew Tarzia,

Wentao Shan,

Víctor Posligua

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Heteroleptic (mixed‐ligand) coordination cages are of interest as host systems with more structurally and functionally complex cavities than homoleptic architectures. The design heteroleptic cages, however, is far from trivial. In this work, we experimentally probed the self‐assembly Pd(II) ions binary ligand combinations in a combinatorial fashion to search for new cis ‐Pd 2 L L’ cages. A hierarchy computational analyses was then applied these aim elucidating key factors rationalising outcomes. Simple inexpensive geometric were shown be effective identifying complementary pairs. Preliminary results demonstrated viability relatively rapid semi‐empirical calculations predicting topology thermodynamically favoured assemblies rigid ligands, whilst flexible proved challenging. Stemming this, challenges identified future work developing forecasting tools self‐assembled metallo‐supramolecular systems.

Language: Английский

Heteromeric Completive Self-Sorting in Coordination Cage Systems DOI
Élie Benchimol, Irene Regeni,

Bo Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6905 - 6911

Published: Feb. 29, 2024

Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations homoleptic precursors. Based on the latter approach, we here describe new level self-sorting in cage systems, namely, 'heteromeric completive self-sorting'. Here, two heteroleptic assemblies type Pd2A2B2 and Pd2A2C2, sharing one common ligand component A but differing other, are shown to coexist solution. This reached either statistical mixture based some ligands B C or, alternatively, following first step integrative giving distinct Pd2B2C2 intermediate. While subtle enthalpic factors dictate outcome self-sorting, found that it is controllable. From unique three demonstrate transition strict forming Pd2AB2C heteromeric give Pd2A2C2 variation ratio. Cage-to-cage were followed NMR MS experiments. Single crystal X-ray structures for cages obtained, impressively highlighting versatility form π-stacked trans-figure-of-eight arrangement occupy cis-edges only single edge Pd2AB2C. study paves way toward control populations systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, stimuli-responsive catalytic action.

Language: Английский

Citations

19
Supramolecular and molecular capsules, cages and containers DOI Creative Commons

C. Cox,

Jessica Hale,

Paulina Molinska

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(21), P. 10380 - 10408

Published: Jan. 1, 2024

Stemming from early seminal notions of molecular recognition and encapsulation, three-dimensional, cavity-containing capsular compounds assemblies have attracted intense interest due to the ability modulate chemical physical properties species encapsulated within these confined spaces compared bulk environments. With such a diverse range covalent motifs non-covalent (supramolecular) interactions available assemble building blocks, an incredibly wide-range capsular-type architectures been developed. Furthermore, synthetic tunability internal environments gives chemists opportunity engineer systems for uses in sensing, sequestration, catalysis transport molecules, just name few. In this tutorial review, overview is provided into design principles, synthesis, characterisation, structural facets coordination cages, porous organic supramolecular capsules, foldamers mechanically interlocked molecules. Using recent examples, advantages limitations each system are explored, highlighting their application various tasks functions.

Language: Английский

Citations

11
The multifaceted roles of MnL2n cages in catalysis DOI
Zoe Ashbridge, Joost N. H. Reek

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(10), P. 1197 - 1207

Published: July 24, 2024

Language: Английский

Citations

9
Highly Anisotropic Pd2Lab2Lcc2 and Pd2Lab2Lcd2 Type Cages by Heteromeric Completive Self‐Sorting DOI

Minaz Parbin,

Vellaiyadevan Sivalingam, Dillip Kumar Chand

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 20, 2024

Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such utilize either more than one type symmetrical ligands (e.g., L

Language: Английский

Citations

7
The cutting edge of lantern-shaped cage methodologies DOI

Zack T. Avery,

Jess L. Algar, Dan Preston

et al.

Trends in Chemistry, Journal Year: 2024, Volume and Issue: 6(7), P. 352 - 364

Published: April 9, 2024

Language: Английский

Citations

5
Host–guest complexation‐induced chirality switching of pillararenes by perylene diimide‐based hexagonal metallacages DOI Creative Commons

Yali Hou,

Chaoqun Mu,

Yunzhi Shi

et al.

Aggregate, Journal Year: 2024, Volume and Issue: unknown

Published: June 27, 2024

Abstract Chirality in confined nanospaces has brought some new insights into chirality transfer, amplification, and chiroptical properties. However, switching, which is a common phenomenon biological systems, never been realized environments. Herein, we report type of hexagonal metallacages that shows good host–guest interactions with ethoxy pillar[5]arene pillar[6]arene, as confirmed by single‐crystal X‐ray analysis. Importantly, when chiral pillar[5]arene‐based molecular universal joint (MUJ) used the guest, complexation would drive alkyl ring MUJ flip from outside to inside cavity its unit, enables configuration change along inversion MUJ. Moreover, facilitates transfer guests hosts, giving circularly polarized luminescence system. This study provides unique metallacage‐pillararene recognition motif for switching planar pillararenes, will promote construction systems tunable advanced applications.

Language: Английский

Citations

5
The beauty of low symmetry: Non-statistical assembly of [Pd2(LA)(LB)(LC)(LD)]4+ cages DOI Creative Commons
L Faulkner, James D. Crowley

Chem, Journal Year: 2024, Volume and Issue: 10(2), P. 440 - 442

Published: Jan. 31, 2024

Language: Английский

Citations

4
Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors DOI Creative Commons
Yonggang Tan,

Lumei Zhang,

Qixia Bai

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Precise endo -functionalization tailors the host cavity to fit shape and charge distribution of target guest molecules, offering a novel bottom-up strategy for constructing customized molecular receptors.

Language: Английский

Citations

0
Configurational Control of Low-Symmetry Heteroleptic Metal-Organic Cages with Asymmetric Ligands DOI Creative Commons
Hao Yu,

Ziteng Guo,

Jie Tang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Two heteroleptic cages were constructed by combining asymmetric ligand assembly with multi-ligand co-assembly strategies. The introduction of methyl group enables configurational transformation and directed into a single configuration.

Language: Английский

Citations

0
Dissecting the Effects of Cage Structure in the Catalytic Activation of Imide Chlorenium-Ion Donors DOI Creative Commons
Hang Zhou, Tomasz K. Piskorz, Keyu Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Imide-based chlorinating reagents are mild and easy to use yet can lack the reactivity of charged chlorenium-ion donors. Here, we present a simple strategy for increasing these neutral species by encapsulation inside cationic coordination cage. Using this approach, demonstrate that two different-sized Pd2L4 cages catalyze chlorolactonization chlorocycloetherification reactions acid alcohol functionalized α β-substituted styrene substrates with either 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) or N-chlorosuccinimide (NCS) as chlorenium sources. A kinetic study shows proficient catalysts significant acceleration up 105. However, an unexpected dichotomy is revealed wherein smaller cage, which best preorganized bind nominally provide maximum activation imide reagent, order magnitude less than larger cage has apparently mismatched host–guest chemistry. When scope further extended chlorination simple, unfunctionalized α-methylstyrene, same pattern observed, suggesting differences not explained coencapsulation. Computational studies indicate trend in caused transition state being fixed allowing it find optimal binding thereby generate stronger interactions. This investigation highlights importance understanding underlying mechanisms design new noncovalent greater range transformations.

Language: Английский

Citations

0