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

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
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
Synthesis, characterization and biological activity of binuclear palladium(II) complexes DOI Creative Commons
Debakanta Tripathy, Soumya Lipsa Rath, Niladri Bihari Debata

et al.

Results in Chemistry, Journal Year: 2025, Volume and Issue: 15, P. 102310 - 102310

Published: April 28, 2025

Language: Английский

Citations

0
London Dispersion driven Compaction of Coordination Cages in the Gas-phase – A combined Ion Mobility and Theoretical Study DOI Creative Commons

Christoph Drechsler,

Ananya Baksi,

André Platzek

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(46), P. 19264 - 19272

Published: Jan. 1, 2024

Large self-assembled systems (such as metallosupramolecular rings and cages) can be difficult to structurally characterize, in particular when they show a highly dynamic behavior.

Language: Английский

Citations

1
Orientational Compatibility Modulation of Ligands in Low‐Symmetry Multi‐Cavity Discrete Coordination Cages by Neighbouring Cage Participation DOI Open Access
Ashish Kumar, Shobhana Krishnaswamy, Dillip Kumar Chand

et al.

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

Published: Oct. 19, 2024

Complexation of Pd(II) with a designer unsymmetrical bis-monodentate ligand (2 : 4 ratio) yielded specific Pd

Language: Английский

Citations

1
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

Citations

0