Synergizing Steric Hindrance and Stacking Interactions to Facilitate the Controlled Assembly of Multiple 41 Metalla‐Knots and Pseudo‐Solomon Links DOI
Guo‐Xin Jin,

Yan Zou,

Shu-Jin Bao

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 5, 2024

Abstract In this work, a noncoplanar terphenyl served as building block to synthesize novel 3,3′‐substituted bipyridyl ligand ( L1 ) which further reacted with binuclear half‐sandwich units A/B , giving rise two aesthetic 4 1 metalla‐knots in high yields via coordination‐driven self‐assembly strategy. Furthermore, given the inherent compactness of metalla‐knots, it creates favorable conditions for emergence steric repulsion. We focused on progressively introducing nitrogen atoms featuring lone pair electrons (LPEs) into manipulate balance H⋅⋅⋅H/LPEs⋅⋅⋅LPEs repulsion during assembly process, ultimately achieving controlled from pseudo ‐Solomon link and then molecular tweezer‐like facilitated by stacking interactions. All assemblies were well characterized solution‐state NMR techniques, ESI‐TOF/MS, single‐crystal X‐ray diffraction. The evolutionary process topological architectures is equivalent visualizing synergistic effect hindrance interactions structural assembly, providing new avenue synthesis different topologies.

Language: Английский

Guest-induced topological transformation and near-infrared photothermal conversion featuring the Cp*Rh unit via coordination-driven self-assembly DOI
Xinyu Wang,

Qiu‐Shui Mu,

Xiang Gao

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

Citations

2
Shape‐Complementary Multicomponent Assembly of Low‐Symmetry Co(III)Salphen‐Based Coordination Cages DOI Creative Commons
Bo Zhang, Haeri Lee, Julian J. Holstein

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 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.

Language: Английский

Citations

8
Synergizing Steric Hindrance and Stacking Interactions to Facilitate the Controlled Assembly of Multiple 41 Metalla‐Knots and Pseudo‐Solomon Links DOI
Guo‐Xin Jin,

Yan Zou,

Shu-Jin Bao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 20, 2024

In this work, a noncoplanar terphenyl served as building block to synthesize novel 3,3'-substituted bipyridyl ligand (L1) which further reacted with binuclear half-sandwich units A/B, giving rise two aesthetic 4

Language: Английский

Citations

4
Ionic Radius-Dependent Self-Assembly of Lanthanide Organic Polyhedra: Structural Diversities and Luminescent Properties DOI
Jing Su, Fan Yin,

Xiao‐Fang Duan

et al.

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

Published: Jan. 1, 2025

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

Language: Английский

Citations

0
Dissecting the Effects of Cage Structure in the Catalytic Activation of Imide Chlorenium-Ion Donors DOI Creative Commons
Hang Zhou, Tomasz K. Piskorz, Keyu Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Imide-based chlorinating reagents are mild and easy to use yet can lack the reactivity of charged chlorenium-ion donors. Here, we present a simple strategy for increasing these neutral species by encapsulation inside cationic coordination cage. Using this approach, demonstrate that two different-sized Pd2L4 cages catalyze chlorolactonization chlorocycloetherification reactions acid alcohol functionalized α β-substituted styrene substrates with either 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) or N-chlorosuccinimide (NCS) as chlorenium sources. A kinetic study shows proficient catalysts significant acceleration up 105. However, an unexpected dichotomy is revealed wherein smaller cage, which best preorganized bind nominally provide maximum activation imide reagent, order magnitude less than larger cage has apparently mismatched host–guest chemistry. When scope further extended chlorination simple, unfunctionalized α-methylstyrene, same pattern observed, suggesting differences not explained coencapsulation. Computational studies indicate trend in caused transition state being fixed allowing it find optimal binding thereby generate stronger interactions. This investigation highlights importance understanding underlying mechanisms design new noncovalent greater range transformations.

Language: Английский

Citations

0
3D fractal expanding of a Sierpiński triangular-faced supramolecular cage for enhanced photocatalytic performance DOI
Zhilong Jiang,

Qiaolin Chen,

Min Wang

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111168 - 111168

Published: April 1, 2025

Language: Английский

Citations

0
Programmable Self-Sorting within a Library of Metal–Organic Cages DOI

Zhao Ma,

Jiajia Zhang, Chunmiao Ma

et al.

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

Published: May 29, 2025

Self-sorting exerts a pivotal role in biological self-assembly processes, enabling the hierarchical organization of biomacromolecules with exquisite selectivity. Inspired by nature, we present programmable supramolecular coordination system where two types ligands undergo sequential narcissistic and social self-sorting events to assemble either homoleptic or heteroleptic metal-organic cages. Homoleptic cage formation proceeds through rigid flexible ligands, depending on their varying sizes, whereas cages emerge self-sorting, adaptive conformational adjustments achieve geometric complementarity counterparts. Notably, this sorting behavior exhibits progressive enhancement ligand size expansion, facilitating cascaded when alternating components along dimensional gradient are sequentially introduced. Furthermore, introduction hydrogen-bonding constraints modifies flexibility capacity, thereby redirecting pathways toward distinct outcomes. This study lays foundation for advancing field systems chemistry, emphasizing potential developing multistage assembly cascades.

Language: Английский

Citations

0
Flexibility and Dynamicity Enhances and Controls Supramolecular Self‐Assembly of Zinc(II) Metallogels DOI Creative Commons

Merlin R. Stühler,

Hesam Makki, Dorothee Silbernagl

et al.

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

Published: June 1, 2025

Abstract Supramolecular self‐assembly of stacked architectures is typically achieved through hydrogen bonding or π–π interactions between monomers constructed from stable and inert bonds. In contrast, coordinative early metals promise distinct behaviour due to more flexible geometries a wider range stabilities exchange kinetics. this report we demonstrate that tailoring the coordination sphere Zinc(II) complexes via subtle ligand modification promotes not only one but also three‐dimensional both thermodynamically kinetically into higher‐order fibrous morphologies, latter being elucidated by electron tomography. As result, chemistry can be translated nanoscopic (fibre stiffness) macroscopic (thermal gel stability) material properties. Utilizing dynamicity enables gelation subcomponent self‐assembly, constructing supramolecular polymer network simultaneously with monomer. Furthermore, dis‐ reassembly metal‐ligand reactions involving first second spheres allows for control over emission system. Our links concepts in leveraging unique cannot traditional monomers, promising applications stimuli‐responsive optoelectronics.

Language: Английский

Citations

0
Double-Bridging Increases the Stability of Zinc(II) Metal–Organic Cages DOI Creative Commons

Hannah Kurz,

Paula C. P. Teeuwen, Tanya K. Ronson

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30958 - 30965

Published: Nov. 4, 2024

A key feature of coordination cages is the dynamic nature their coordinative bonds, which facilitates synthesis complex polyhedral structures and post-assembly modification. However, this can limit cage stability. Increasing robustness important for real-world use cases. Here we introduce a double-bridging strategy to increase stability, where designed pairs bifunctional subcomponents combine generate rectangular tetratopic ligands within pseudo-cubic Zn8L6 cages. These withstand transmetalation, addition competing ligands, nucleophilic imines, under conditions single-bridged congeners decompose. Our approach not only increases stability while maintaining structure, but also enables incorporation additional functional units in proximity cavity. The larger cages, are inaccessible as congeners.

Language: Английский

Citations

1
Formkomplementäre Multikomponenten Assemblierung von Niedrigsymmetrischen Co(III)Salphen Koordinationskäfigen DOI Creative Commons
Bo Zhang, Haeri Lee, Julian J. Holstein

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(24)

Published: April 4, 2024

Abstract Während die metallvermittelte Selbstassemblierung eine beliebte Methode zur Synthese definierter Nanoobjekte ist, wird Literatur von hochsymmetrischen Strukturen, aufgebaut aus jeweils einer Art Liganden, dominiert. Die kontrollierte Integration Reihe verschiedener Liganden erfordert ausgeklügelte Ansätze, um narzisstische Trennung oder Bildung statistischer Mischungen zu vermeiden. Hier zeigen wir, wie Kombination drei strukturleitenden Effekten (metallvermittelte Makrozyklisierung, zusätzliches Anbringen Brückenliganden und Formkomplementarität) auf der Grundlage Co(III)salphen‐Metallzentren rationale laternenförmigen Käfigen mit bis vier differenzierbaren Brücken ermöglicht. Drei neue heteroleptische Koordinationskäfige, basierend zweikernigen Co(III)salphen‐Makrozyklen, wurden in Eintopfreaktion synthetisiert vollständig charakterisiert, einschließlich Einkristall‐Röntgenstrukturanalysen. Einer Käfige gruppiert zwei gleiche ein anderer verschiedene einen symmetrischen Co 2 ‐Bis‐Salphen‐Ring. In komplexesten Struktur ist dieser Ring unsymmetrisch, so dass alle zwischen den beiden Metallzentren unterscheidbar sind. sich Assemblies Pd(II)‐Zentren als dynamisch vorteilhaft für Käfig‐zu‐Käfig‐Umwandlungen adaptive Systeme erwiesen haben, werden hier vorgestellten kinetisch stabileren Co(III)‐Salphen Einheiten Anwendungen, erhöhte strukturelle chemische Stabilität erfordern, Vorteil sein, z.B. enzymähnlichen Katalyse molekularen Maschinen.

Citations

0