A Cu^I₆L₄ Cage Dynamically Reconfigures to Form Suit[4]anes and Selectively Bind Fluorinated Steroids

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10234 - 10239

Опубликована: Апрель 5, 2024

Simple organic ligands can self-assemble with metal ions to generate metal–organic cages, whose cavities bind guests selectively. This binding may enable new methods of chemical separation or sensing, among other useful functions. Here we report the preparation a CuI6L4 pseudo-octahedral cage, which from simple building blocks. Temperature, solvent, and presence different governed structure predominated dynamic mixture cage diastereomers arrangements right- left-handed vertices. Dissolution in dimethyl sulfoxide tetrahedral led chiral T-symmetric framework, whereas low temperatures favored achiral S4-symmetric diastereomer. Tetrahedral long arms were encapsulated form mechanically bonded suit[4]anes, guest protruding out through host windows. The was also observed fluorinated steroids, an important class drug molecules, but not non-fluorinated providing basis for processes.

Язык: Английский

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54 K Spin Transition Temperature Shift in a Fe₆L₄ Octahedral Cage Induced by Optimal Fitted Multiple Guests

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7811 - 7821

Опубликована: Март 7, 2024

Spin-crossover (SCO) coordination cages are at the forefront of research for their potential in crafting next-generation molecular devices. However, due to scarcity SCO hosts and own limited cavities, interplay between host multiple guests binding has remained elusive. In this contribution, we present a family pseudo-octahedral (M6L4, M = ZnII, CoII, FeII, NiII) assembled from tritopic tridentate ligand L with metal ions. The utilization FeII ion leads successful creation Fe6L4-type cage. Host–guest studies these M6L4 reveal capacity encapsulate four adamantine-based guests. Notably, spin transition temperature T1/2 Fe6L4 is dependent on encapsulated. inclusion adamantine yields an unprecedented shift 54 K, record guest-mediated date. This drastic ascribed synergistic effect coupled optimal fit within host. Through straightforward thermodynamic cycle, affinities high-spin (HS) low-spin (LS) states separated apparent constant. result indicates that LS state stronger affinity than HS state. Exploring thermodynamics host–guest complexes allows us examine cavity. study reveals can be manipulated by encapsulation guests, cage ideal candidate determining guest fit.

Язык: Английский

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Supramolecular and molecular capsules, cages and containers

Chemical Society Reviews, Год журнала: 2024, Номер 53(21), С. 10380 - 10408

Опубликована: Янв. 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.

Язык: Английский

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Cage‐To‐Cage Transformations in Self‐Assembled Coordination Cages Using “Acid/Base” or “Guest Binding‐Induced Strain” as Stimuli

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 3, 2024

Abstract Controlling supramolecular systems between different functional forms by utilizing acids/bases as stimuli is a formidable challenge, especially where labile coordination bonds are involved. A pair of acid/base responsive, interconvertible 1,5‐enedione/pyrylium based Pd 2 L 4 ‐type cages prepared that exhibit differential guest binding abilities towards disulfonates varied sizes. three‐state switch has been achieved, (i) weakly coordinating base induced cage‐to‐cage transformation in the first step, (ii) strongly triggered cage disassembly second and (iii) third step shows acid(strong) promoted generation initial cage, thereby completing cycle. To our surprise, specific disulfonate facilitated transformations inducing strain on assembly opening pyrylium rings cage. Through competitive study, we demonstrated superior capability octacationic pyrylium‐based over similar‐sized tetracationic These results provide reliable approach to reversibly modulate properties acid/base‐responsive self‐assembled cages.

Язык: Английский

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Highly selective synthesis and near-infrared photothermal response of heterometallic double trefoil knot and D-type [2]catenanes

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Язык: Английский

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Magnetic and Porous Regulation in Cobalt(II) Hydrogen-Bonded Organic Framework via Supramolecular Isomerism

Crystal Growth & Design, Год журнала: 2024, Номер 24(8), С. 3449 - 3457

Опубликована: Апрель 2, 2024

Supramolecular isomerism has been recognized as an effective strategy for manipulating structures and properties, particularly in metal–hydrogen-bonded organic frameworks (MHOFs). However, it less studied the context of magnetic dynamics. In this study, we reinvestigated two previously reported cobalt(II) HOFs, {[(H2O)2Co(Hbic)2]·sol}n (H2bic = 1H-benzimidazole-5-carboxylic acid; 1, Sol 2DMF·1.5H2O; 2, H2O), which exhibit unique supramolecular isomerism. both complexes, octahedral Co(II) ions are connected by deprotonated Hbic-ligands to form one-dimensional chains, then sustained into three-dimensional prominent N–H···O hydrogen-bonding interactions. This results significantly different porosities N2-adsorption abilities: a high solvent-accessible void 46.2% desolvated phase compared only 2.3% that likely due additional π–π stacking Interestingly, our studies revealed 1 2 typical single ion magnet behaviors, with alternating relaxation dynamics (Raman, direct, QTM 1; Raman direct 2). These findings demonstrate structures, stability, porosities, properties MHOF materials can be effectively tuned through isomerization approach.

Язык: Английский

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Innovative supramolecular coordination nanomedicine: Targeting inflammation and scavenging ROS for synergistic arthritis therapy

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160644 - 160644

Опубликована: Фев. 1, 2025

Язык: Английский

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Ionic Radius-Dependent Self-Assembly of Lanthanide Organic Polyhedra: Structural Diversities and Luminescent Properties

Inorganic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This article presents the influence of lanthanide size and ligands conformational flexibility on assemblies their corresponding luminescent properties.

Язык: Английский

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Revisiting the Origins of Reactivity and Selectivity in the Pd₆L₄-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Supramolecular metal–organic cages (MOCs) have gained attention as versatile catalytic platforms due to their self-assembled architectures and well-defined cavities, which mimic enzyme active sites enable spatial confinement. This confinement modulates the reaction pathways enhances performance. Recent studies highlight potential in various organic transformations, but factors governing MOC-catalyzed reactions remain incompletely understood. work builds on prior computational of Diels–Alder catalyzed by palladium-based MOCs, showing that common view transition-state stabilization via π–π interactions is not valid. Instead, we find between substrate ligands destabilize transition state. Additionally, theoretical regioselectivity, validated experimentally, suggest encapsulation efficiency key determining selectivity. These findings provide new insights into mechanisms reactions.

Язык: Английский

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Supramolecular Eu(III)₄L₄ Tetrahedra-Based Films for Luminescence Sensing of Volatile Amines with Sub-ppt-Level Detection Limit

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Metal–organic cages are a class of discrete supramolecular architectures endowed with well-defined cavity and diverse functionalities, offering broad range applications that, however, predominantly confined to liquid phases. In this study, we present the self-assembly Eu(III)4L4 tetrahedra, constructed from triarylborane-cored tritopic tridentate ligands, which were fabricated into spin-coated films bright emission, smooth surfaces, uniform thickness. These demonstrated ultralow detection limits for series volatile amines, reaching sub-ppt level. This work serves as compelling example preparation application metal–organic-cage-based films, paving way broader scenarios.

Язык: Английский

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