Hetero- and Homointerlocked Metal–Organic Cages

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3147 - 3159

Published: Jan. 27, 2024

Interlocked molecular assemblies constitute a captivating ensemble of chemical topologies, comprising two or more separate components that exhibit remarkably intricate structures. The interlocked are typically identical, and heterointerlocked systems comprise structurally distinct remain unexplored. Here, we demonstrate metal-templated synthesis can be exploited to afford not only homointerlocked cage but also cage. Treatment carboxylated 2,9-dimethyl-1,10-phenanthroline (dmp) Cu(I) bis-dmp linker with Ni

Language: 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, Journal Year: 2024, Volume and Issue: 146(11), P. 7811 - 7821

Published: March 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.

Language: Английский

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Triamine and Tetramine Edge-Length Matching Drives Heteroleptic Triangular and Tetragonal Prism Assembly

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5215 - 5223

Published: Feb. 13, 2024

Heteroleptic metal–organic capsules, which incorporate more than one type of ligand, can provide enclosed, anisotropic interior cavities for binding low-symmetry molecules biological and industrial importance. However, the selective self-assembly a single mixed-ligand architecture, as opposed to numerous other possible outcomes, remains challenge. Here, we develop design strategy subcomponent heteroleptic architectures with internal void spaces. Zn6Tet3Tri2 triangular prismatic Zn8Tet2Tet′4 tetragonal were prepared through careful matching side lengths tritopic (Tri) or tetratopic (Tet, Tet′) panels.

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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Incorporation of Chiral Frustrated Lewis Pair into Metal–Organic Framework with Tailored Microenvironment for Heterogeneous Enantio- and Chemoselective Hydrogenation

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(8), P. 1692 - 1701

Published: July 27, 2023

The development of efficient heterogeneous catalysts with multiselectivity (e.g., enantio- and chemoselectivity) has long been sought after but limited progress being made so far. To achieve chemoselectivity in a system, as inspired by enzymes, we illustrate herein an approach creating enzyme-mimic region (EMR) within the nanospace metal–organic framework (MOF) exemplified context incorporating chiral frustrated Lewis pair (CFLP) into MOF tailored pore environment. Due to high density EMR featuring active site CFLP auxiliary sites hydroxyl group/open metal vicinity CFLP, resultant EMR@MOF demonstrated excellent catalysis performance hydrogenation α,β-unsaturated imines afford β-unsaturated amines yields chemoselectivity. role regulating was proved observation catalyst–substrate interaction experimentally, which also rationalized computational results. This work not only contributes new platform for multiselective opens promising avenue develop challenging yet important transformations.

Language: Английский

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Supramolecular Assembly Frameworks (SAFs): Shaping the Future of Functional Materials

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 7, 2024

Supramolecular assembly frameworks (SAFs) represent a new category of porous materials, utilizing non-covalent interactions, setting them apart from metal-organic (MOFs) and covalent organic (COFs). This includes but is not restricted to hydrogen-bonded supramolecular frameworks. SAFs stand out for their outstanding porosity, crystallinity, stability, alongside unique dissolution-recrystallization dynamics that enable significant structural functional modifications. Crucially, strategies allow balanced manipulation symmetry, dimensions, facilitating the creation advanced crystalline materials unattainable through conventional or coordination bond synthesis. Despite considerable promise in overcoming several limitations inherent MOFs COFs, particularly terms solution-processability, have received relatively little attention recent literature. Minireview aims shed light on standout SAFs, exploring design principles, synthesis strategies, characterization methods. It emphasizes distinctive features broad spectrum potential applications across various domains, aiming catalyze further development practical application within scientific community.

Language: Английский

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Functional Post-Synthetic Chemistry of Metal–Organic Cages According to Molecular Architecture and Specific Geometry of Origin

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 462 - 462

Published: Jan. 21, 2025

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers; MOCs noted for their high porosity processability. Chemically, they can be post-synthetically modified (PSM) new functional groups introduced, presenting attractive qualities, it is expected that properties will differ from those the original compound. This why highly regarded in fields biology chemistry. The present review deals with current PSM strategies used MOCs, including covalent, coordination, noncovalent methods structural benefits. main emphasis this to show what extent under circumstances a MOC designed obtain tailored geometric architecture. Although sometimes unclear when examining systems, particularizing design systematic approaches development characterization families provides insights into structure–function relationships, which guide future developments.

Language: Английский

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A Highly Luminescent Metallo-Supramolecular Radical Cage

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24081 - 24088

Published: Oct. 5, 2023

Luminescent metal-radicals have recently received increasing attention due to their unique properties and promising applications in materials science. However, the luminescence of tends be quenched after formation metallo-complexes. It is challenging construct with highly luminescent properties. Herein, we report a metallo-supramolecular radical cage (LMRC) constructed by assembly tritopic terpyridinyl ligand RL tris(2,4,6-trichlorophenyl)methyl (TTM) Zn2+. Electrospray ionization-mass spectrometry (ESI-MS), traveling-wave ion mobility-mass (TWIM-MS), X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) confirm prism-like supramolecular cage. LMRC exhibits remarkable photoluminescence yield (PLQY) 65%, which 5 times that RL; meanwhile, also shows high photostability. Notably, significant magnetoluminescence can observed for high-concentration (15 wt % doped PMMA film); however, 0.1 film vanishes, revealing negligible spin-spin interactions between two centers LMRC.

Language: Английский

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Dynamic Stereochemistry of M₈Pd₆ Supramolecular Cages Based on Metal‐Center Lability for Differential Chiral Induction, Resolution, and Recognition

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Oct. 26, 2023

Abstract A series of isostructural supramolecular cages with a rhombic dodecahedron shape have been assembled distinct metal‐coordination lability (M 8 Pd 6 ‐MOC‐16, M=Ru 2+ , Fe Ni Zn ). The chirality transfer between metal centers generally imposes homochirality on individual to enable solvent‐dependent spontaneous resolution Δ / Λ −M enantiomers; however, their distinguishable stereochemical dynamics manifests differential chiral phenomena governed by the cage stability following order Ru > . highly labile endow conformational flexibility and deformation, enabling intrigue chiral‐ −Zn meso‐ 4 transition induced anions. stabilization effect differs from inert metastable /Ni resulting in different chiral‐guest induction. Strikingly, solvent‐mediated host–guest interactions revealed for −(Ru/Ni/Fe) discriminate recognition guests opposite chirality. These results demonstrate versatile procedure control stereochemistry metal‐organic based dynamic centers, thus providing guidance maneuver at level virtue solvent, anion, guest benefit practical applications.

Language: Английский

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Cofacial porphyrin organic cages. Metals regulating excitation electron transfer and CO₂ reduction electrocatalytic properties

Chemical Science, Journal Year: 2023, Volume and Issue: 14(34), P. 9086 - 9094

Published: Jan. 1, 2023

A comprehensive study of the photophysical behaviors and CO 2 reduction electrocatalytic properties a series cofacial porphyrin organic cages reveals metals regulate excitation electron transfer properties.

Language: Английский

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