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

Integrating spin-dependent emission and dielectric switching in FeII catenated metal-organic frameworks DOI Creative Commons
Xue-Ru Wu, Shu‐Qi Wu, Zhikun Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 10, 2024

Abstract Mechanically interlocked molecules (MIMs) including famous catenanes show switchable physical properties and attract continuous research interest due to their potential application in molecular devices. The advantages of using spin crossover (SCO) materials here are enormous, allowing for control through diverse stimuli highly specific functions, enabling the transfer internal dynamics MIMs from solution solid state, leading macroscopic applications. Herein, we report efficient self-assembly catenated metal-organic frameworks (termed catena-MOFs) induced by stacking interactions, combination rationally selected flexible conjugated naphthalene diimide-based bis-pyridyl ligand (BPND), [M I (CN) 2 ] − (M = Ag or Au) Fe 2+ a one-step strategy. obtained bimetallic Hofmann-type SCO-MOFs [Fe II (BPND){Ag(CN) } ]·3CHCl 3 ( 1Ag ) (BPND{Au(CN) ]·2CHCl ·2H O 1Au possess unique three-dimensional (3D) catena-MOF constructed polycatenation two-dimensional (2D) layers with hxl topology. Both complexes undergo thermal- light-induced SCO. Significantly, abnormal increases maximum emission intensity dielectric constant can be detected simultaneously switching states. This opens up SCO-actuated bistable that afford dual functionality coupled fluorescence dielectricity.

Language: Английский

Citations

18
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
Selective Construction and Structural Transformation of Homogeneous Linear Metalla[4]catenane and Metalla[2]catenane Assemblies DOI
Wei‐Long Shan,

Huan‐Huan Hou,

Nian Si

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 7, 2024

Abstract Although the synthesis of mechanically interlocked molecules has been extensively researched, selectively constructing homogeneous linear [4]catenanes remains a formidable challenge. Here, we constructed metalla[4]catenane in one‐step process through coordination‐driven self‐assembly bidentate benzothiadiazole derivative ligand and binuclear half‐sandwich rhodium precursor. The formation metalla[4]catenanes was facilitated by cooperative interactions between strong sandwich‐type π‐π stacking non‐classical hydrogen bonds components. Moreover, modulating aromatic substituents on precursor, two metalla[2]catenanes were obtained. molecular structures these metallacatenanes unambiguously characterized single‐crystal X‐ray diffraction analysis. Additionally, reversible structural transformation metal‐catenanes corresponding metallarectangles could be achieved altering their concentration, as confirmed mass spectrometry NMR spectroscopy studies.

Language: Английский

Citations

10
Self-Assembly and Dynamic Equilibrium of Trinuclear and Tetranuclear Cu(I) Supramolecules Featuring nido-Carborane-Supported N-Heterocyclic Carbene Ligands DOI

Yun-Kang Ren,

Yiwen Li,

Mei-Juan Liang

et al.

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

Published: May 8, 2025

The self-assembly of metallo-supramolecules has attracted considerable attention in recent decades. These discrete architectures are primarily driven by coordination interactions, typically involving M-N/O (Werner-type) or M-C (organometallic) bonding. However, the use M-π interactions for constructing these multinuclear complexes remains largely unexplored. In this work, we report trinuclear and tetranuclear copper(I) a combination interactions. Cu(I)-NHC were synthesized from nido-carborane-supported N-heterocyclic carbene (NHC) precursors Cu(I) ions. solution, dynamic equilibrium between species was observed, as confirmed variable-temperature NMR spectrum. Van't Hoff analysis revealed that is endothermic (ΔHeq = 53.6 kJ mol-1) entropically (ΔSeq 158 J mol-1 K-1). solid-state structures both forms elucidated through single-crystal XRD analysis. Density functional theory calculations showed Cu-CNHC bonds relatively weak (∼100 mol-1, approximately one-third strength typical bonds). This attributed to strong Coulombic attraction positively charged negatively nido-carborane ligands (M-π interactions), which significantly reduces bond neutral NHC moieties (M-C bonding).

Language: Английский

Citations

1
Selective Synthesis and Structural Transformation of a 4‐Ravel Containing Four Crossings and Featuring Cp*Rh/Ir Fragments DOI

Li‐Long Dang,

Tingting Zhang, Tian Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 17, 2023

Intricately interwoven topologies are continually being synthesized and ultimately equally versatile significant at the nanoscale level; however, reports concerning ravel structures, which highly entwined new topological species, extremely rare fraught with tremendous synthesis challenges. To solve problem, a tetrapodontic pyridine ligand L1 two types of olefinic bond units Cp*M-based building blocks (E1, M=Rh; E2, M=Ir) featuring large conjugated planes was prepared to perform self-assembly. Two unprecedented [5+10] icosanuclear molecular 4-ravels containing four crossings were obtained by parallel-displaced π⋅⋅⋅π interactions in single-step strategy. Remarkably, reversible structural transformations between 4-ravel corresponding metallocage could be realized concentration changes solvent- guest-induced effects. X-ray crystallographic data NMR spectroscopy provide full confirmation these phenomena.

Language: Английский

Citations

23
Selective construction of molecular Solomon links and figure-eight knots by fine-tuning unsymmetrical ligands DOI

Qiu‐Shui Mu,

Xiang Gao, Zheng Cui

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(10), P. 2885 - 2891

Published: Sept. 7, 2023

Language: Английский

Citations

23
Cross-catenation between position-isomeric metallacages DOI Creative Commons
Yiliang Wang, Taotao Liu, Yangyang Zhang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 14, 2024

Abstract The study of cross-catenated metallacages, which are complex self-assembly systems arising from multiple supramolecular interactions and hierarchical assembly processes, is currently lacking but could provide facile insights into achieving more precise control over low-symmetry/high-complexity systems. Here, we report a cross-catenane formed between two position-isomeric Pt(II) metallacages in the solid state. These [2]catenanes solution, whereas 1:1 mixture selectively crystals. Varied temperature nuclear magnetic resonance experiments time-of-flight mass spectra employed to characterize cross-catenation solutions, dynamic library shown. Additionally, searched for global-minimum structures three re-optimized low-lying using density functional theory calculations. Our results suggest that binding energy cross-catenanes significantly larger than self-catenanes within library, selectivity crystallization thermodynamic. This presents different may insight development self-assemble

Language: Английский

Citations

9
Synthesis of a Metalla[2]catenane, Metallarectangles and Polynuclear Assemblies from Di(N‐Heterocyclic Carbene) Ligands DOI Creative Commons

Jin-Ping Chang,

Ya‐Wen Zhang, Li‐Ying Sun

et al.

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

Published: Aug. 16, 2024

The 2,7-fluorenone-linked bis(6-imidazo[1,5-a]pyridinium) salt H

Language: Английский

Citations

7
Size-controlled synthesis and near-infrared photothermal response of Cp* Rh-based metalla[2]catenanes and rectangular metallamacrocycles DOI
Ying Zhao,

Yin‐Hang Chai,

Tian Chen

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(6), P. 109298 - 109298

Published: Nov. 13, 2023

Language: Английский

Citations

14
Highly Efficient Self‐Assembly of Heterometallic [2]Catenanes and Cyclic Bis[2]catenanes via Orthogonal Metal‐Coordination Interactions DOI
Feng Qian, Rui Ding,

Yali Hou

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 13, 2024

Although catenated cages have been widely constructed due to their unique and elegant topological structures, cyclic catenanes formed by the connection of multiple catenane units rarely reported. Herein, based on orthogonal metal-coordination-driven self-assembly, we prepare a series heterometallic [2]catenanes bis[2]catenanes, whose structures are clearly evidenced single-crystal X-ray analysis. Owing positively charged nature, as well potential synergistic effect Cu(I) Pt(II) metal ions, bis[2]catenanes display broad-spectrum antibacterial activity. This work not only provides an efficient strategy for construction but also explores applications superior agents, which will promote advanced supramolecular biomedical applications.

Language: Английский

Citations

5