The dynamic regulation of supramolecular chirality in non-equilibrium systems can provide valuable insights into molecular self-assembly in living systems. Herein, we demonstrate the use of chemical fuels for regulating self-assembly pathway, which thereby controls the supramolecular chirality of assembly in non-equilibrium systems. Depending on the nature of different fuel acids, the system shows pathway-dependent non-equilibrium self-assembly, resulting in either dynamic self-assembly with transient supramolecular chirality or kinetically trapped self-assembly with inverse supramolecular chirality. More importantly, successive conducting of chemical-fueled process and thermal annealing process allows for the sequential programmability of the supramolecular chirality between four different chiral hydrogels, affording a new example of a multistate supramolecular chiroptical switch that can be recycled multiple times. The current finding sheds new light on the design of future supramolecular chiral materials, offering access to alternative self-assembly pathways and kinetically controlled non-equilibrium states.
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http://dx.doi.org/10.1038/s41467-023-40698-9 | DOI Listing |
Materials (Basel)
January 2025
College of Chemistry, Sichuan University, Chengdu 610064, China.
Circularly polarized luminescence (CPL) is an emerging field with significant applications in molecular electronics, optical materials, and chiroptical sensing. Achieving efficient CPL emission in organic systems remains a major challenge, particularly in the development of materials with high fluorescence quantum yields (Φ) and large luminescence dissymmetry factors (g). Herein, we report the efficient synthesis of shape-persistent tetraphenylethylene macrocycles and investigate its potential as a CPL material.
View Article and Find Full Text PDFOrg Chem Front
December 2024
Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid Av. Complutense S/N 28040 Madrid Spain
Supramolecular chemistry of carbon-based materials provides a variety of chemical structures with potential applications in materials science and biomedicine. Here, we explore the supramolecular complexation of fullerenes C and C, highlighting the ability of molecular nanographene tweezers to capture these structures. The binding constant for the CNG-1⊃C complex was significantly higher than for CNG-1⊃C, showing a clear selectivity for the more π-extended C.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
The birth and development of supramolecular chemistry have heralded a new era, where macrocycles have become an irreplaceable research tool. Therefore, the construction of novel macrocycles has become a hot spot. Tröger's base (TB), as a fragment with both rigidity and chirality, promises tremendous potential in the realm of supramolecular chemistry, and its unique properties continue to motivate researchers to explore its inclusion in macrocycles.
View Article and Find Full Text PDFNature
January 2025
Department of Chemistry, The University of Hong Kong, Hong Kong SAR, China.
Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids and ferritin offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C-H hydrogen bonds.
View Article and Find Full Text PDFNat Chem
January 2025
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA.
Atomically precise nanoclusters can be assembled into ordered superlattices with unique electronic, magnetic, optical and catalytic properties. The co-crystallization of nanoclusters with functional organic molecules provides opportunities to access an even wider range of structures and properties, but can be challenging to control synthetically. Here we introduce a supramolecular approach to direct the assembly of atomically precise silver nanoclusters into a series of nanocluster‒organic ionic co-crystals with tunable structures and properties.
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