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

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

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Solvent-Induced Magnetic Properties of a Series of Dy-Based MOFs from Two Different Precursor Complexes

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(22), P. 9692 - 9700

Published: Nov. 4, 2024

It is still challenging for Dy-MOFs to modulate the single-molecule magnet (SMM) behavior through guest molecules. with different molecules, secondary building units, and linkers were synthesized by precursors bridging carboxylic acid ligands, magnetic properties of regulated These differentiated are [Dy2(C9H4Cl2NO)2(L1)2(H2O)(DMA)]n·DMA (MOF-3, L1 = terephthalate), [Dy(C9H4Cl2NO)2(L1)(DMSO)(H2O)]n (MOF-4), [Dy2(C9H4Br2NO)2(L1)2(H2O)(DMA)]n·DMA (MOF-5), [Dy(C9H4Cl2NO)2(L2)(H2O)]n·DMA (MOF-6, L2 isophthalate), [Dy(C9H4Cl2NO)2(L2)(H2O)]n·DMF (MOF-7), [Dy(C9H4Br2NO)2(L2)(H2O)]n·DMA (MOF-8). The single-crystal X-ray diffraction showed that MOF-3 MOF-5 two-dimensional MOFs square holes. MOF-4 a MOF formed hydrogen–halogen bonds, MOF-6, MOF-7, MOF-8 one-dimensional chains. test results show MOF-4, SMM under zero field, exhibit field-induced behavior. In effective energy bases 37.09, 19.56, 15.73 K, relaxation times τ0 4.66 × 10–6, 2.35 9.95 10–6 s, respectively. This work provides vivid example regulating molecular magnetism promotes progress Dy-MOF crystal engineering.

Language: Английский

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A Coordination-Driven Self-Assembly and NIR Photothermal Conversion Study of Organometallic Handcuffs

Molecules, Journal Year: 2023, Volume and Issue: 28(19), P. 6826 - 6826

Published: Sept. 27, 2023

Due to their fascinating topological structures and application prospects, coordination supramolecular complexes have continuously been studied by scientists. However, the controlled construction property study of organometallic handcuffs remains a significant challenging research subject in area chemistry. Hence, series tetranuclear heterometallic bearing different size metal types were rationally designed successfully synthesized utilizing quadridentate pyridyl ligand (tetra-(3-pyridylphenyl)ethylene) based on three Cp*Rh (Cp* = η5-C5Me5) fragments specific longitudinal dimensions conjugated planes. These results determined with single-crystal X-ray diffraction analysis technology, ESI-MS NMR spectroscopy, etc. Importantly, photoquenching effect Cp* groups discrepancy intermolecular π-π stacking interactions between building block half-sandwich promote markedly photothermal conversion results. will further push synthesis development materials.

Language: Английский

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