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Macrocyclic arenes have emerged as pivotal scaffolds in supramolecular chemistry. Despite their significant contributions to molecular recognition and diverse applications, challenges persist in the development of macrocyclic arene-based crystalline materials, particularly in achieving porosity and addressing limitations in adsorption efficiency resulting from the small cavity sizes of existing macrocyclic arenes. In this study, we present the design and synthesis of a novel macrocyclic arene, clamparene (), featuring a rigid backbone, easy synthesis, and a sizable cavity. self-assembles into one-dimensional sub-nanotubes that further organize into a three-dimensional porous framework in the solid state. The crystalline solid of exhibits potential as a porous crystalline adsorbent for various benzene-based contaminants with rapid adsorption kinetics, large uptake amounts, and good recyclability.
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http://dx.doi.org/10.1021/jacs.3c13714 | DOI Listing |
J Am Chem Soc
September 2025
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China.
Metal-organic frameworks (MOFs) are distinguished by their structural diversity, tunable electronic properties, and exceptional performance in various applications. Notably, the electron-donating ability of ligands significantly enhances the ligand-to-metal charge transfer (LMCT) processes within these frameworks, thereby promoting efficient charge migration. Herein, we developed two electron-rich macrocyclic ligands derived from phenothiazine- and phenoxazine-functionalized calix[3]arenes, alongside their corresponding cobalt-coordinated MOFs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, 310058, P.R. China.
Mechanoresponsive molecular devices are capable of exhibiting dynamic responses to external mechanical stimuli, enabling applications in smart materials, nano-devices, and flexible electronics. However, energy conversion induced by mechanical stimuli requires efficient energy dissipation mechanisms. Traditional methods often involve bond breaking or incomplete energy release, which can lead to device failure during continuous operations.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, 1139 Shifu Road, Taizhou, Zhejiang 318000, China.
Here, intramolecular hydrogen bond (IMHBs)-induced rigidity is used for the first time to synthesize macrocyclic arenes. Calix[]azanediyldibenzoates (C[]A, where = 3, 4, or 5) are synthesized through a one-step condensation reaction between dimethyl 2,2'-azanediyldibenzoate and paraformaldehyde. Compared to the monomer, the macrocycles exhibit a fast and significant acidochromic response due to the intramolecular charge transfer that is boosted by the synergistic effect of their adsorption and protonation.
View Article and Find Full Text PDFSmall Methods
September 2025
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
Microspheres have emerged as a pivotal platform for micron-scale drug delivery, yet their utility has been greatly hindered by limitations in biodegradability, drug loading efficiency, and release kinetics, underscoring the urgent need for a next-generation microsphere platform that integrates high performance, scalability, and multifunctionality. Leveraging host-guest recognition, a series of macrocycle-incorporated polymers is synthesized and engineered a new class of supramolecular microspheres, which feature precisely tunable components, including host molecules, guest cargoes, and polymer components, as well as customizable morphologies, while enabling cost-effective, large-scale production. Following systematic validation of the host-guest recognition between β-cyclodextrin (β-CD) and lanreotide, we developed supramolecular microspheres (LAN@S-CPMs) that achieve a drug loading capacity and release duration approximately twice that of conventional microspheres, effectively curbing the disease progression of acromegaly.
View Article and Find Full Text PDFAcc Chem Res
August 2025
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland.
ConspectusAlkynes are one of the most fundamental functional groups in organic synthesis due to the versatile chemistry of the triple bond, their unique rigid structure, and their use in bioconjugation. The introduction of alkynes onto organic molecules traditionally relies on nucleophilic activation, often requiring strong bases or metal catalysts. These conditions, however, restrict applications involving biomolecules such as peptides and proteins due to functional group incompatibility.
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