Water-Soluble Self-Assembled Cage with Triangular Metal–Metal-Bonded Units Enabling the Sequential Selective Separation of Alkanes and Isomeric Molecules

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 16191 - 16198

Published: Aug. 16, 2022

The selective separation of structurally similar aliphatic/aromatic hydrocarbons is an essential goal in industrial processes. In this study, we report the synthesis a water-soluble (Tr2M3)4L4 (Tr = cycloheptatrienyl ring; M metal; L organosulfur ligand) molecular cage (1) via self-assembly acceptor tripalladium sandwich species [(Tr2Pd3)(CH3CN)][NO3]2 and attachment onto solubilizing methoxyethoxy appendants to be utilized energy-friendly alternative approach molecules under ambient conditions. Cage 1, comprising hydrophobic inner cavity, exhibited good solubility stability aqueous media. It also demonstrated excellent performance sequential alkanes (C6–C9), xylene, other disubstituted benzene isomers cis/trans-decalin.

Language: Английский

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Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 19, 2024

Abstract The self‐assembled metal‐organic cages (MOCs) have been evolved as a paradigm of enzyme‐mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components constitute microenvironments characteristic enzymatic spatial confinement versatile host–guest interactions, thus facilitating unconventional transformations via unique driving‐forces such weak noncovalent binding electron/energy transfer. Recently, MOC‐based photoreactors emerged burgeoning platform supramolecular photocatalysis, displaying anomalous reactivities selectivities distinct from bulk solution. This perspective recaps two decades journey the photoinduced radical reactions by using photoactive (PMOCs) artificial reactors, outlining how cage‐confined photocatalysis was stoichiometric photoreactions photocatalytic turnover, high‐energy UV‐irradiation sustainable visible‐light photoactivation, simple multi‐level chemo‐ stereoselectivities. We will focus on PMOCs that merge structural functional biomimicry into single‐cage behave multi‐role photoreactors, emphasizing their potentials tackling current challenges through single‐electron transfer (SET) or energy (EnT) pathways simple, green while feasible manner.

Language: Английский

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Metallacages and Covalent Cages for Biological Imaging and Therapeutics

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(4), P. 1061 - 1082

Published: March 8, 2023

Due to their precise three-dimensional structures and tunable cavities, metallacages covalent cages have been widely used in various fields, such as catalysis, separation, sensing, biomedicine. As a result of the unique pattern directed synthesis modular assembly, can be modified many different ways construct stimuli-responsive for marker detection imaging biological applications. Additionally, agents drugs loaded into cavity achieve disease diagnosis treatment. This Review summarizes recent advances applications presents representative examples therapeutics. The problems future development directions are emphasized, which may provide clear guidance design application controllable diagnostic reagents.

Language: Английский

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Unveiling Confinement Engineering for Achieving High‐Performance Rechargeable Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 7, 2024

Abstract The confinement effect, restricting materials within nano/sub‐nano spaces, has emerged as an innovative approach for fundamental research in diverse application fields, including chemical engineering, membrane separation, and catalysis. This principle recently presents fresh perspectives on addressing critical challenges rechargeable batteries. Within spatial confinement, novel microstructures physiochemical properties have been raised to promote the battery performance. Nevertheless, few clear definitions specific reviews are available offer a comprehensive understanding guide utilizing effect review aims fill this gap by primarily summarizing categorization of effects across various scales dimensions systems. Subsequently, strategic design environments is proposed address existing These solutions involve manipulation physicochemical electrolytes, regulation electrochemical activity, stability electrodes, insights into ion transfer mechanisms. Furthermore, provided deepen foundational achieving high‐performance Overall, emphasizes transformative potential tailoring microstructure electrode materials, highlighting their crucial role designing energy storage devices.

Language: Английский

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Regulation of lanthanide supramolecular nanoreactors via a bimetallic cluster cutting strategy to boost aza-Darzens reactions

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 4, 2025

Supramolecular nanoreactor as artificial mimetic enzyme is attracting a growing interest due to fine-tuned cavity and host-guest molecular recognition. Here, we design three 3d-4f metallo-supramolecular nanocages with different sizes active sites (Zn2Er4L14, Zn4Er6L26, Zn2Er8L38) based on "bimetallic cluster cutting" strategy. Three exhibit differential catalysis for the three-component aza-Darzens reaction without another additive, only Zn2Er8L38 largest most lanthanides centers has excellent catalytic conversion monosubstituted disubstituted N-aryl aziridine products. The relationship investigations confirm that significantly outperforms Zn2Er4L14 smaller Zn4Er6L26 fewer Lewis acidic in multi-component mainly attributed synergy of inherent confinement effect multiple nanocage. strategy construction large windows may represent potential approach develop supramolecular high efficiency.

Language: Английский

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An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 29, 2022

Artificial hosts with rich conformational dynamics are attractive to supramolecular chemists due their adaptive guest-binding properties and enzyme-like catalytic functions. We report here the self-assembly host-guest catalysis of a new water-soluble organo-palladium host (Pd2 L2 ) built from pyridinium-bonded macrocyclic ligand (L) cis-blocked palladium corners (Pd). While direct L Pd gives rise dynamic mixture products, both neutral polyaromatic hydrocarbons an anionic polyoxometalate cluster (W10 O324- can template dominant formation Pd2 host. Guest-adaptive changes induced-fit cavity deformation have been clearly observed in crystal structures. Moreover, installation electron-rich W10 within cationic redox-active O32 ⊂Pd2 facilitates efficient selective C-H photooxidation toluene derivatives aldehyde products under mild conditions, thus representing ideal platform for green catalysis.

Language: Английский

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Controlled Self-Assembly, Isomerism, and Guest Uptake/Release of Charge-Reversible Lanthanide–Organic Octahedral Cages

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 17845 - 17855

Published: Aug. 7, 2023

Charge plays a crucial role in the function of molecular and supramolecular systems, but coordination hosts capable orthogonal charge regulation remain elusive so far. In this study, we report condition-dependent self-assembly charge-reversible lanthanide–organic tetra-capped octahedral cages, i.e., [Ln6(H3L)4]6+ [Ln6L4]6–, from series lanthanide ions (Ln3+; Ln = Lu, Yb, Eu) tritopic tetradentate acylhydrazone ligand (H6L) featuring multiple deprotonation states propeller conformations. While direct under basic conditions produced mixture various ΔxΛ6–x-[Ln6L4]6– (x 0–6) stereoisomers, racemic Δ6- Λ6-[Ln6L4]6– could be exclusively obtained first Λ6-[Ln6(H3L)4]6+ neutral followed by post-assembly deprotonation. Rich isomerism on cages arising coupling between metal-centered Δ/Λ chirality conformations has been discussed based X-ray single-crystal structures C3-symmetric Δ3Λ3-Ln6L4 T-symmetric Δ6/Λ6-Ln6L4 complexes. Host–guest studies confirmed that positively charged rac-Δ6/Λ6-[Ln6(H3L)4]6+ bind anionic sulfonates, negatively rac-Δ6/Λ6-[Ln6L4]6– exhibited strong encapsulation ability toward ammonium guests, where acid/base-triggered guest uptake/release realized taking advantage reversibility cage. Moreover, photophysical revealed visible-light-sensitized guest-encapsulation-enhanced NIR emissions rac-Δ6/Λ6-Yb6L4 This work not only enriches library functional also provides promising candidate with for development smart materials.

Language: Английский

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Heterometallic supramolecular polymers: From synthesis to properties and applications

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 501, P. 215573 - 215573

Published: Dec. 12, 2023

Language: Английский

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Modular Construction of AIE-Active Supramolecular Cages with Tunable Fluorescence for NIR-II Blood Vessel Imaging

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(8), P. 1982 - 1991

Published: June 26, 2023

Fluorescent supramolecular cages have attracted significant scientific interest owing to their widespread applications in molecular sensing, luminescent materials, and biological systems. However, the modular construction of such assemblies with tunable emission behaviors affording high-performance bioimaging is still challenging. Herein, we developed a general straightforward protocol formulate an aggregation-induced (AIE) tendency by using "donor–acceptor–donor (D–A–D)" adducts as building blocks. A series box-shaped MA–MG adjustable fluorescence from red second near-infrared (NIR-II) region were successfully prepared. In particular, maximum MG was located at 981 nm, behaving like rare NIR-II emissive thus far, cage-loaded nanoparticles MGNPs featured high absolute quantum yield region, which enabled them perform well blood vessel imaging.

Language: Английский

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Cavity‐Directed Synthesis of Labile Polyoxometalates for Catalysis in Confined Spaces

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Feb. 26, 2024

Abstract The artificial microenvironments inside coordination cages have gained significant attention for performing enzyme‐like catalytic reactions by facilitating the formation of labile and complex molecules through a “ship‐in‐a‐bottle” approach. Despite many fascinating examples, this approach remains scarcely explored in context synthesizing metallic clusters such as polyoxometalates (POMs). development innovative approaches to control influence speciation POMs aqueous solutions would greatly advance their applicability could ultimately lead elusive that cannot be synthesized using traditional methods. In study, we employ host–guest stabilization within cage enable novel cavity‐directed synthesis under mild conditions. Lindqvist [M 6 O 19 ] 2− (M=Mo or W) were successfully at room temperature via condensation molybdate tungstate building blocks confined cavity robust water‐soluble Pt L 4 (NO 3 ) 12 cage. Importantly, encapsulation these enhances stability water, rendering them efficient catalysts environmentally friendly selective sulfoxidation H 2 green oxidant pure medium. developed paper offers means synthesize stabilize otherwise unstable metal‐oxo which can broaden scope applications.

Language: Английский

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