Adaptive Planar Chirality of Pillar[5]arenes Invertible by n-Alkane Lengths

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8114 - 8121

Опубликована: Март 28, 2023

Chirality of host molecules can be induced and/or inverted by the guest molecules. However, adapting chirality hosts to length n-alkanes remains a great challenge because are neutral, achiral, and linear molecules, resulting in weak interaction with most compounds. Herein, we report system adapted n-alkane lengths, using pillar[5]arene-based macrocyclic host, S-Br, which contains five stereogenic carbons terminal bromine atoms on each rim. The electron-rich cavity S-Br could include planar-chiral isomers sensitively response lengths complexed n-alkanes. inclusion short such as n-pentane made more inclined pS-form, whereas long n-heptane pR-form favorable. difference stability was supported crystal structures theoretical calculations. Furthermore, temperature drives adaptive An middle length, n-hexane, showed dominance at higher temperature, pS-form shown lower temperature.

Язык: Английский

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Predesigned Cluster-Based Spacers for Versatile Luminescent Metallacages

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 13514 - 13519

Опубликована: Июнь 12, 2023

Luminescent metal–organic cages are of great interest in contemporary research; however, their designed synthesis remains challenging. Here, we created metal-cluster-derived spacers, where emissive C3-symmetric Cu4 clusters have three arms modified by benzene alkynyl ligands, which terminally functionalized extensile −COOH and 15-crown-5-ether groups with directional coordination ability. Through vertex orientation, −COOH-functionalized cluster-based spacers coassembled paddle-wheel Cu(I)xZn(II)2-x(COO)3 nodes 3+3 mode, generating an cubic cage, subsequently gave another distorted cage synthetic modification on the nodes. face 15-crown-5-ether-containing capturing K+ ions 3+2 mode produced octahedral whose empty phase showed dual emission peaks, leading to diverse stimuli-responsive photoluminescence. This work provides new design strategies for integration based metal materials as well prototypes luminescent metal-cluster important sensing applications.

Язык: Английский

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Controlled Self-Assembly, Isomerism, and Guest Uptake/Release of Charge-Reversible Lanthanide–Organic Octahedral Cages

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17845 - 17855

Опубликована: Авг. 7, 2023

Charge plays a crucial role in the function of molecular and supramolecular systems, but coordination hosts capable orthogonal charge regulation remain elusive so far. In this study, we report condition-dependent self-assembly charge-reversible lanthanide–organic tetra-capped octahedral cages, i.e., [Ln6(H3L)4]6+ [Ln6L4]6–, from series lanthanide ions (Ln3+; Ln = Lu, Yb, Eu) tritopic tetradentate acylhydrazone ligand (H6L) featuring multiple deprotonation states propeller conformations. While direct under basic conditions produced mixture various ΔxΛ6–x-[Ln6L4]6– (x 0–6) stereoisomers, racemic Δ6- Λ6-[Ln6L4]6– could be exclusively obtained first Λ6-[Ln6(H3L)4]6+ neutral followed by post-assembly deprotonation. Rich isomerism on cages arising coupling between metal-centered Δ/Λ chirality conformations has been discussed based X-ray single-crystal structures C3-symmetric Δ3Λ3-Ln6L4 T-symmetric Δ6/Λ6-Ln6L4 complexes. Host–guest studies confirmed that positively charged rac-Δ6/Λ6-[Ln6(H3L)4]6+ bind anionic sulfonates, negatively rac-Δ6/Λ6-[Ln6L4]6– exhibited strong encapsulation ability toward ammonium guests, where acid/base-triggered guest uptake/release realized taking advantage reversibility cage. Moreover, photophysical revealed visible-light-sensitized guest-encapsulation-enhanced NIR emissions rac-Δ6/Λ6-Yb6L4 This work not only enriches library functional also provides promising candidate with for development smart materials.

Язык: Английский

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Allosterically Regulated Guest Binding Determines Framework Symmetry for an Fe^II₄L₄ Cage

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Март 3, 2023

Abstract Self‐assembly of a flexible tritopic aniline and 3‐substituted 2‐formylpyridine subcomponents around iron(II) templates gave rise to low‐spin Fe II 4 L capsule, whereas high‐spin 3 2 sandwich species formed when sterically hindered 6‐methyl‐2‐formylpyridine was used. The cage adopted new structure type with S symmetry, having two mer ‐ Δ Ʌ metal vertices, as confirmed by NMR X‐ray crystallographic analysis. flexibility the face‐capping ligand endows resulting framework conformational plasticity, enabling it adapt structurally from T or C symmetry upon guest binding. also displayed negative allosteric cooperativity in simultaneously binding different guests within its cavity at apertures between faces.

Язык: Английский

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Metallacycle/metallacage-cored supramolecular networks

Progress in Polymer Science, Год журнала: 2023, Номер 141, С. 101680 - 101680

Опубликована: Апрель 23, 2023

Язык: Английский

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