Controlling bottom-up syntheses from chiral seeds to construct architectures with specific chiralities is currently challenging. Herein, a twisted chiral cavitand with 5-fold symmetry was constructed by bottom-up synthesis using corannulene as the chiral seed and pillar[5]arene as the chiral wall. After docking between the seed and the wall, their dynamic chiralities ( and ) are fixed. Moreover, the formed hedges also exhibit and chirality. Through dynamic covalent bonding, the thermodynamically stable product is obtained selectively as a pair of enantiomers ( and ), where all three subcomponents, i.e., the corannulene, hedges, and pillar[5]arene, are tilted in the same direction. Furthermore, the twisted cavitand exhibits length-selective binding to alkylene dibromides, with three maximum binding constants being unexpectedly observed.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.2c11225 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules.
Nat Commun
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing, China.
Helicene-shaped molecules are compelling chemical structures with unique twisted helical chirality and remarkable properties. Although progress occurs in the catalytic asymmetric synthesis of helicene (-like) molecules, the enantioselective synthesis of multiple helicenes, especially four or higher helicity, is still challenging and has yet to be achieved. Herein, we report an organocatalytic [4 + 2] cycloadditions to achieve double S-shaped quadruple helicene-like molecules with high enantioselectivity (up to 96% e.
View Article and Find Full Text PDFMechanical Twisting-Induced Enhancement of Second-Order Optical Nonlinearity in a Flexible Molecular Crystal.
J Am Chem Soc
January 2025
School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecular Materials Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tongyan Road 38, Tianjin 300350, P. R. China.
Flexible molecular crystals are essential for advancing smart materials, providing unique functionality and adaptability for applications in next-generation electronics, pharmaceuticals, and energy storage. However, the optical applications of flexible molecular crystals have been largely restricted to linear optics, with nonlinear optical (NLO) properties rarely explored. Herein, we report on the application of mechanical twisting of flexible molecular crystals for second-order nonlinear optics.
View Article and Find Full Text PDFThermal Actuators Relying on Elastomer-Dispersed Liquid Crystals: From Imines with Supramolecular Chirality and Ferroelectricity to Soft Robots.
ACS Appl Mater Interfaces
January 2025
Department of Inorganic Polymers, "Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, 700487 Iasi, Romania.
The locomotion of various organisms relies on the alternated elongation-contraction of their muscles or bodies. Such biomimicry can offer a promising approach to developing soft robotic devices with improved mobility and efficiency. Most strategies to mimic such motions rely on reversible size modifications of some materials upon exposure to external stimuli.
View Article and Find Full Text PDFIntrinsic and Extrinsic Photogalvanic Effects in Twisted Bilayer Graphene.
Phys Rev Lett
December 2024
Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastian, Spain.
The chiral lattice structure of twisted bilayer graphene with D_{6} symmetry allows for intrinsic photogalvanic effects only at off-normal incidence, while additional extrinsic effects are known to be induced by a substrate or a gate potential. In this Letter, we first compute the intrinsic effects and show they reverse sign at the magic angle, revealing a band inversion at the Γ point. We next consider different extrinsic effects, showing how they can be used to track the strengths of the substrate coupling or electric displacement field.
View Article and Find Full Text PDFScrolled Poly(L-lactic acid) Single Crystals via Chain End-Induced Symmetry-Breaking.
Angew Chem Int Ed Engl
January 2025
The University of Tennessee Knoxville, Chemistry, UNITED STATES OF AMERICA.
Article Synopsis
- Single crystals that lack translational symmetry have been observed in different materials, particularly in polymers where unique structures like twisted crystals and non-flat single crystals appear.
- Researchers have discovered scrolled single crystals of poly(L-lactic acid) (PLLA), a biodegradable polymer, which differ from the typical flat crystals formed in solution.
- The scrolled structure of PLLA crystals is influenced by factors such as the polymer's molecular weight and the presence of polymer chain ends, suggesting a novel mechanism for disrupting translational symmetry in the growth of polymer single crystals.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!