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

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Окт. 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.

Язык: Английский

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

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21196 - 21202

Опубликована: Июль 25, 2024

A heteroleptic [Pd

Язык: Английский

Процитировано

23
Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering** DOI Creative Commons
Paulina Molinska, Andrew Tarzia, Louise Male

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(51)

Опубликована: Окт. 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

Язык: Английский

Процитировано

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

8
Highly Anisotropic Pd2Lab2Lcc2 and Pd2Lab2Lcd2 Type Cages by Heteromeric Completive Self‐Sorting DOI

Minaz Parbin,

Vellaiyadevan Sivalingam, Dillip Kumar Chand

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 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

Язык: Английский

Процитировано

7
Origins of High-Activity Cage-Catalyzed Michael Addition DOI Creative Commons

Patrick J. Boaler,

Tomasz K. Piskorz, Laura E. Bickerton

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19317 - 19326

Опубликована: Июль 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.

Язык: Английский

Процитировано

5
Diastereoselective Supramolecular Encapsulation and Chirality Transfer Between Cholesteryl Binaphthyl Conjugates and Polyaromatic Hydrocarbon DOI
Qi Zhang,

Aiyou Hao,

Pengyao Xing

и другие.

Small, Год журнала: 2024, Номер 20(35)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

3
Discrete metallosupramolecular architectures with amino acids DOI Creative Commons
Shannon Thoonen, Kellie L. Tuck, David R. Turner

и другие.

Coordination Chemistry Reviews, Год журнала: 2024, Номер 522, С. 216203 - 216203

Опубликована: Сен. 11, 2024

Язык: Английский

Процитировано

3
Solvent-Directed Social Chiral Self-Sorting in Pd2L4 Coordination Cages DOI Creative Commons
Alexandre Walther, Gers Tusha,

Björn Schmidt

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32748 - 32756

Опубликована: Ноя. 17, 2024

A family of Pd2L4 cages prepared from ligands based on an axially chiral diamino-[1,1′-biazulene] motif (serving as a unique azulene-based surrogate the ubiquitous BINOL moiety) is reported. We show that preparing cage starting racemate shorter bis-monodentate ligand derivative, equipped with pyridine donor groups, leads to integrative ("social") self-sorting, exclusively yielding meso-trans product, but only in selection solvents. This phenomenon driven by individual solvent molecules acting hydrogen bonding tethers between amino groups neighboring ligands, thereby locking final coordination single isomeric form. The experimental (solvent-dependent NMR, single-crystal X-ray diffraction) observations this cooperative interaction could be explained computational analyses when explicit solvation was considered. Furthermore, we larger isoquinoline donors, which, unlike first one, does not undergo social self-sorting its racemic mixture, further highlighting importance solvents bridging short distances groups. Homochiral formed ligand, however, furnish cavity can bind anionic and neutral metal complexes such [Pt(CN)6]2– Cr(CO)6 discriminate two enantiomers guest camphor sulfonate.

Язык: Английский

Процитировано

3
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

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

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

Ziteng Guo,

Jie Tang

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

0