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

et al.

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

Published: Oct. 19, 2024

Abstract Complexation of Pd(II) with a designer unsymmetrical bis‐monodentate ligand (2 : 4 ratio) yielded specific Pd 2 L type “single‐cavity discrete coordination cage” (SCDCC), from pool isomeric structures. The observed selctivity is attributed to inherent orientational preference the strands around metal centers. Crafting short coordinating arm at either ends (i.e longer‐arm) produced pair tris‐monodentate ligands; whereas crafting same short‐arm both gives an tetrakis‐monodentate ligand. tris‐monodenate ligands (3 resulted in corresponding low‐symmetry “multi‐cavity MCDCC having two conjoined cavities, though relative longer arms not achievable these cages. enforced orientation sustained by “Neighbouring Cage Participation” (NCP). However, one‐pot combination Pd(II), mixture 3 ratio integratively self‐sorted mixed‐ligated 31 Also, mixing three cavities. longer‐arm retained double‐cavity and homo‐ligated triple cavity

Language: Английский

Photoswitchable Catalysis by a Self-Assembled Molecular Cage DOI Creative Commons
Ray G. DiNardi, Samina Rasheed, Simona S. Capomolla

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21196 - 21202

Published: July 25, 2024

A heteroleptic [Pd

Language: Английский

Citations

22
Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering** DOI Creative Commons
Paulina Molinska, Andrew Tarzia, Louise Male

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Oct. 27, 2023

Metal-organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low-symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate use primary coordination-sphere engineering (CSE) bias selectivity within homo- heteroleptic Pd

Language: Английский

Citations

21
Shape‐Complementary Multicomponent Assembly of Low‐Symmetry Co(III)Salphen‐Based Coordination Cages DOI Creative Commons
Bo Zhang, Haeri Lee, Julian J. Holstein

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 4, 2024

Abstract While metal‐mediated self‐assembly is a popular technique to construct discrete nanosized objects, highly symmetric structures, built from one type of ligand at time, are dominating reported systems. The tailored integration set different ligands requires sophisticated approaches avoid narcissistic separation or formation statistical mixtures. Here, we demonstrate how the combination three structure‐guiding effects (metal‐templated macrocyclization, additional bridging and shape‐complementarity) based on Co(III)salphen metal nodes allows for rational high‐yielding synthesis structurally complex, lantern‐shaped cages with up four differentiable bridges. Three new heteroleptic coordination dinuclear macrocycles were synthesized in one‐pot reaction approach fully characterized, including single crystal X‐ray analyses. One cage groups two same ligands, another around Co 2 ‐bis‐salphen ring. In most complex structure, this ring unsymmetric, rendering all connections between centers distinguishable. assembly Pd(II) has been shown be dynamic, beneficial cage‐to‐cage transformations, cascades adaptive systems, herein introduced kinetically more inert will advantageous applications enzyme‐like catalysis molecular machinery that require enhanced structural chemical stability.

Language: Английский

Citations

7
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

6
Origins of High-Activity Cage-Catalyzed Michael Addition DOI Creative Commons

Patrick J. Boaler,

Tomasz K. Piskorz, Laura E. Bickerton

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19317 - 19326

Published: July 8, 2024

Cage catalysis continues to create significant interest, yet catalyst function remains poorly understood. Herein, we report mechanistic insights into coordination-cage-catalyzed Michael addition using kinetic and computational methods. The study has been enabled by the detection of identifiable intermediates, which allow evolution different cage species be monitored modeled alongside reactants products. investigations show that overall acceleration results from two distinct effects. First, reaction shows a thousand-fold increase in rate constant for turnover-limiting C–C bond-forming step compared reference state. Computational modeling experimental analysis activation parameters indicate this stems reduction entropy, suggesting substrate coencapsulation. Second, markedly acidifies bound pronucleophile, shifting equilibrium up 6 orders magnitude. combination these factors accelerations 109 relative bulk-phase reactions. We also can fundamentally alter mechanism, leading intermediates products are not observable outside cage. Collectively, proceed with very high activity unique selectivity harnessing series individually weak noncovalent interactions.

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
Discrete metallosupramolecular architectures with amino acids DOI Creative Commons
Shannon Thoonen, Kellie L. Tuck, David R. Turner

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 522, P. 216203 - 216203

Published: Sept. 11, 2024

Language: Английский

Citations

3
Diastereoselective Supramolecular Encapsulation and Chirality Transfer Between Cholesteryl Binaphthyl Conjugates and Polyaromatic Hydrocarbon DOI
Qi Zhang,

Aiyou Hao,

Pengyao Xing

et al.

Small, Journal Year: 2024, Volume and Issue: 20(35)

Published: April 29, 2024

Abstract Diastereoselective effect plays an important role in the synthesis of chiral complexes and macrocyclic compounds, while its function selective coassembly chirality transfer has yet to be unveiled. In this work, two pairs diastereomers containing R/S‐ binaphthyl homochiral cholesteryl domains are synthesized, which provide multiple sites encapsulate polyaromatic hydrocarbon through π–π CH–π interactions. X‐ray structures computational studies suggest binaphthol derivatives feature folding into butterfly‐like open geometry, binaphthylenediamine adopt closed geometry supported by van der Waals between domains. Driven solvophobic forces, building units self‐assemble vesicles nanofibers aqueous methanol phases, respectively. Binaphthol selectively pyrene naphthalene vesicle phase, nanofiber phase. Density functional theory‐based calculations circular dichroism spectra evidence facilitates a clamp‐type host increase affinity toward spite strong solvation competition. This work unveils diastereoselectivity coassembly, deepening understanding precise chiroptical complexes.

Language: Английский

Citations

2