Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters DOI
Xiaowei Qi, YuLong Xie, Jingyang Niu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Oct. 24, 2024

Abstract Heterometallic cluster‐based materials offer the potential to incorporate multiple functionalities, leveraging aggregation effects of clusters and translating this heterogeneity complexity into unexpected properties that are more than just sum their components. However, rational construction heterometallic remains challenging due metal cation coordination structural unpredictability. This minireview provides insights a general synthetic strategy based on Hard Soft Acids Bases (HSAB) theory, summarizing its advantages in designed synthesis discrete (intracluster assembly) infinite (intercluster assembly). Furthermore, it emphasizes exploit intrinsic mixed components achieve breakthroughs across broad range applications. The from review expected drive progress controllable predictable manner.

Language: Английский

A pseudo-cubic metal–organic cage with conformationally switchable faces for dynamically adaptive guest encapsulation DOI Creative Commons
Houyang Xu, Tanya K. Ronson, Andrew W. Heard

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Abstract The creation of hosts capable accommodating different guest molecules may enable these to play useful roles in chemical purifications, among other applications. Metal–organic cages are excellent for various guests, but they generally incorporate rigid structural units that hinder dynamic adaptation specific guests. Here we report a conformationally adaptable pseudo-cubic cage can dynamically increase its cavity volume fit guests with differing sizes. This pseudo-cube incorporates tetramine subcomponent 2,6-naphthalene arms cooperatively adopt non-planar conformation, enabling the faces switch between endo and exo states. A wide range were observed bind within this cage, spanning sizes from 46% 154% empty cage. Experimental computational evidence characterizes flipping , expanding upon binding larger

Language: Английский

Citations

3

Multipocket Cage Enables the Binding of High-Order Bulky and Drug Guests Uncovered by MS Methodology DOI

Yin‐Hui Huang,

Yu‐Lin Lu, Zhong‐Min Cao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21677 - 21688

Published: July 23, 2024

Achieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, drug delivery with synthetic receptors; however, it remains a challenging bottleneck characterization of high-stoichiometry guest-binding events. Herein, we describe large-sized coordination cage (MOC-70-Zn

Language: Английский

Citations

7

Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters DOI

Xiao Qi,

YuLong Xie, Jingyang Niu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Oct. 24, 2024

Heterometallic cluster-based materials offer the potential to incorporate multiple functionalities, leveraging aggregation effects of clusters and translating this heterogeneity complexity into unexpected properties that are more than just sum their components. However, rational construction heterometallic remains challenging due metal cation coordination structural unpredictability. This minireview provides insights a general synthetic strategy based on Hard Soft Acids Bases (HSAB) theory, summarizing its advantages in designed synthesis discrete (intracluster assembly) infinite (intercluster assembly). Furthermore, it emphasizes exploit intrinsic mixed components achieve breakthroughs across broad range applications. The from review expected drive progress controllable predictable manner.

Language: Английский

Citations

6

Activating Metal–Organic Cages by Incorporating Functional M(ImPhen)3 Metalloligands: From Structural Design to Applications DOI
Yu‐Lin Lu, Yaping Wang,

Kai Wu

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(22), P. 3277 - 3291

Published: Oct. 9, 2024

ConspectusThe emulation of ingenious biofunctions has been a research focus for several decades. Metal-organic cages (MOCs), as type discrete supramolecular assembly with well-defined shapes and cavities, have aroused great interest in chemists to imitate natural protein or enzymes. However, genuinely achieve tailored functionalities reactivities enzymes, the design cage structures combining both confined microenvironment active site is prerequisite. Therefore, integration functionalized motifs into MOCs expected provide feasible approach construct biofunctional nanospaces, which not only allows modulation properties applications such molecular recognition, transport, catalysis but also creates unique microenvironments that promote enzymatic effects special selectivities, thereby providing versatile platform exceptional biomimetic functions beyond.In this Account, we specifically on our toward engineering confined-nanospaces via incorporation M(ImPhen)

Language: Английский

Citations

4

Folding encapsulation toward Lindqvist polyoxometalates within adaptive coordination cages for catalysis DOI

Ying-Mei Zhong,

Jin-Jin Xuan,

Xu‐Jie Qin

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Language: Английский

Citations

3

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

Björn Schmidt

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32748 - 32756

Published: Nov. 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.

Language: Английский

Citations

3

Paramagnetic Cage-Type Co(II) Complexes of Chiral Macrocycles: Enantio- and Size-Selective Binding of Guest Molecules DOI Creative Commons
Jan Janczak, Jerzy Lisowski

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 23, 2025

Two enantiomers of the cage-type complex, [Co3LR2] and [Co3LS2] a large hexaazatriphenolic [3 + 3] macrocyclic imine L, have been synthesized characterized on basis NMR, CD, ESI MS spectra. The X-ray crystal structures [Co3L2] crystalline forms reveal two macrocycles cone shape stitched together by three Co(II) ions, forming barrel-shaped molecule with central void. Because limited size cavity enantiopure nature these enantiomeric complexes, both size-selective enantioselective binding guest molecules are observed. In case chiral guests, interaction paramagnetic centers leads to an effective NMR enantiodifferentiation signals molecules, even at host:guest ratios as low 1:200. tight prochiral such ethanol isopropanol within results in splitting enantiotopic methylene methyl signals. dc magnetic data for accord presence high-spin ac susceptibility this complex indicate field-induced single magnet (SMM) behavior. contrast reaction Co(II), ligand H3L Ni(II) or Cu(II) salts contraction macrocycle formation complexes smaller [2 2] macrocycle.

Language: Английский

Citations

0

Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis DOI Creative Commons
Jie Yang, Zhongshu Li,

X.‐M. WU

et al.

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

Published: April 28, 2025

Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, asymmetric photocatalysis unactivated remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined visible-light method for intramolecular dearomative cycloaddition with electron-deficient β-aryl enones. Owing multi-functional synergy chirality, energy transfer, host-guest interactions confined microenvironments, self-assembled chiral cage-photoreactor could pre-organize activate enones give stereoselectively fused cyclobutanes through induced [2 + 2] ortho-cycloaddition. Notably, competing transformation [4 cycloadducts has been inhibited, producing thermodynamically unfavorable excellent regio-, diastereo-, enantioselectivities.

Language: Английский

Citations

0

H2O‐Induced Transformation of Superstructured MOFs into Self‐Standing, Superprotonic Conducting Membranes for Hydrogen Fuel Cells DOI
Xiaoyan Mao, Liang Zhang, Chenchao Xu

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 28, 2025

Abstract Metal–organic frameworks (MOFs) represent an emerging class of crystalline materials characterized by high porosity, vast surface area, and structural variability. Despite the potential for sustainable energy applications, challenges remain in designing engineering MOF powders with limited mechanical robustness integrity into self‐standing, durable membranes while retaining their functionality. Inspired unique structure natural vascular bundles, approach is developed to fabricating via dimensional reduction superstructures. Interestingly, water‐flexibility superstructure led homogeneous gelation, which can encapsulate a substantial amount water molecules within porous structures, forming micro/nano‐scale channels efficient proton transport. Hierarchical channel ensures super‐protonic conductivity values ranging from 0.07 S cm −1 (40% RH) at 293 K 0.14 (90% 353 K. For first time, it demonstrates relevant hydrogen fuel cell performance, achieving peak power density 48 mW −2 . This study paves way all‐MOF‐based as proton‐conducting low‐temperature cells.

Language: Английский

Citations

0

Anion Immobilization from Quasi-Icosahedron to Cubo-Octahedron Enhances the Lithium Ion Transference Number in Solid-State Electrolytes DOI
Zhiyuan Jiang, Huaxin Liu, Lei Fu

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Herein, we report the self-assembly of a D3-symmetric quasi-icosahedron 4 based on desymmetrized terpyridine ligand. The participant triflimide (NTf2-) interacts with rectangular aperture, templating generation 4. With addition other smaller anions (50-90 Å3) into 4, supramolecular conversion to highly symmetric (O) cuboctahedron 5 can be observed due optimizing binding capabilities between and apertures metallo-organic cages. This enables selective tight multiple anion bindings clear mechanism has been utilized facilitate dissociation lithium-anion pairs immobilization in lithium metal batteries. Introducing solid polymer electrolytes increase ion transference number t+ 0.78, significantly enhancing conductivity within electrolyte enriching flux for transport. Consequently, composite exhibits excellent transport kinetics, thereby endowing batteries superior electrochemical performance.

Language: Английский

Citations

0