All-Heteroatom-Substituted Carbon Spiro Stereocenters: Synthesis, Resolution, Enantiomeric Stability, and Absolute Configuration DOI Creative Commons

Olivier Viudes,

Céline Besnard, Alexander F. Siegle

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: June 4, 2025

Chiral tetra-heterosubstituted methanes (i.e., tetraoxa and azatrioxa carbon spiro stereocenters) are synthesized under CpRu catalysis, using cyclic carbonates carbamates as substrates α-diazo-β-ketoesters reagents. Single enantiomers, isolated by chiral stationary phase chromatography, display chiroptical properties, from gabs ∼10-5 to ∼10-4, which, together with TD-DFT calculations, provide robust absolute configuration assignments. Crystalline diastereomers were also obtained, confirming further the structural configurational Using enantioselective dynamic remarkable enantiomerization barriers determined for ortho-carbonates ortho-carbamates, values of up 27.6 34.6 kcal/mol (half-lives 227 days >84,000 years at 25 °C, respectively). DFT elucidates origin this large difference pointing toward preferred C-O or C-N bond cleavages in rate-determining step SN1-like mechanism.

Language: Английский

Reversible Circularly Polarized Luminescence Inversion and Emission Color Switching in Photo-Modulated Supramolecular Polymer for Multi-Modal Information Encryption DOI

Kuo Fu,

Da‐Hui Qu, Guofeng Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Constructing circularly polarized luminescence (CPL) materials that exhibit dynamic handedness inversion and emissive color modulation for multimodal information encryption presents both a significant challenge compelling opportunity. Here, we have developed pyridinethiazole acrylonitrile-cholesterol derivative (Z-PTC) exhibits wavelength-dependent photoisomerization photocyclization, enabling in supramolecular assemblies with decent CPL activity. Coordination Ag

Language: Английский

Citations

7
Circularly Polarized Luminescence from Decamethylcucurbit[5]uril-triggered Chiral Supramolecular Hydrogels DOI
Bing An, Qingmei Ge, Hang Cong

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In the presence of macrocyclic host decamethylcucurbit[5]uril, ternary supramolecular hydrogel materials were achieved, which produced white CPL light via FRET and chirality transfer in systems.

Language: Английский

Citations

0
Highly Photoelectrical responsive and Controllable Supramolecular Helical Assemblies with Dual Functionalities as Photo-Organocatalysts DOI
Yahao Ren, Duo Wei, Wei Yang

et al.

Colloids and Surfaces A Physicochemical and Engineering Aspects, Journal Year: 2025, Volume and Issue: unknown, P. 136968 - 136968

Published: April 1, 2025

Language: Английский

Citations

0
Self-Regulating Hydrogel with Reversible Optical Activity in Its Gel-to-Gel Transformation DOI Creative Commons
Jingjing Li, Yin Fang, Jianhong Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

This study reports a supramolecular gel system capable of dynamic gel-to-gel transformations and reversible inversion optical activity between superhelical single-helical structures without passing through sol phase. Inspired by collagen-like adaptability, the utilizes 4-pyridinylboronic acid guanosine as building blocks. Hierarchical assembly is achieved pH-responsive boronic ester formation guanosine-mediated G-quadruplex stacking, enabling transitions superhelices single helices with opposite activity. The employs three regulatory pathways: bidirectional pH modulation, monotonic increase, decrease, demonstrating programmable control over chirality, morphology, mechanical properties. In autonomous regulation, we have created an out-of-equilibrium hydrogel controlled switching Unlike traditional gel-sol-gel systems, this maintains macroscopic stability during transformations. Our remarkable finding bridges gap static assemblies soft materials, offering platform for designing functional, biomimetic systems. combination hierarchical organization, chirality control, robust programmability positions applications in adaptive optics, responsive biomaterials, matter.

Language: Английский

Citations

0
Development of two semiconducting supramolecular metallogels of Cd(II)- and Hg(II)-ions from 5-aminoisophthalic acid gelator for high-performance Schottky diodes and advanced microelectronic applications DOI Creative Commons
Subhendu Dhibar, Aiswarya Mohan,

Sangita Some

et al.

Deleted Journal, Journal Year: 2025, Volume and Issue: 2(1)

Published: May 12, 2025

Language: Английский

Citations

0
Fabrication of a supramolecular metallogel from citric acid and Mn(II) ions for improved Schottky barrier diode performance in semiconductor devices DOI Creative Commons
Subhendu Dhibar, Aiswarya Mohan,

Saranya Babu

et al.

Deleted Journal, Journal Year: 2025, Volume and Issue: 2(1)

Published: May 13, 2025

Language: Английский

Citations

0
Flexibility and Dynamicity Enhances and Controls Supramolecular Self‐Assembly of Zinc(II) Metallogels DOI Creative Commons

Merlin R. Stühler,

Hesam Makki, Dorothee Silbernagl

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: June 1, 2025

Abstract Supramolecular self‐assembly of stacked architectures is typically achieved through hydrogen bonding or π–π interactions between monomers constructed from stable and inert bonds. In contrast, coordinative early metals promise distinct behaviour due to more flexible geometries a wider range stabilities exchange kinetics. this report we demonstrate that tailoring the coordination sphere Zinc(II) complexes via subtle ligand modification promotes not only one but also three‐dimensional both thermodynamically kinetically into higher‐order fibrous morphologies, latter being elucidated by electron tomography. As result, chemistry can be translated nanoscopic (fibre stiffness) macroscopic (thermal gel stability) material properties. Utilizing dynamicity enables gelation subcomponent self‐assembly, constructing supramolecular polymer network simultaneously with monomer. Furthermore, dis‐ reassembly metal‐ligand reactions involving first second spheres allows for control over emission system. Our links concepts in leveraging unique cannot traditional monomers, promising applications stimuli‐responsive optoelectronics.

Language: Английский

Citations

0
All-Heteroatom-Substituted Carbon Spiro Stereocenters: Synthesis, Resolution, Enantiomeric Stability, and Absolute Configuration DOI Creative Commons

Olivier Viudes,

Céline Besnard, Alexander F. Siegle

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: June 4, 2025

Chiral tetra-heterosubstituted methanes (i.e., tetraoxa and azatrioxa carbon spiro stereocenters) are synthesized under CpRu catalysis, using cyclic carbonates carbamates as substrates α-diazo-β-ketoesters reagents. Single enantiomers, isolated by chiral stationary phase chromatography, display chiroptical properties, from gabs ∼10-5 to ∼10-4, which, together with TD-DFT calculations, provide robust absolute configuration assignments. Crystalline diastereomers were also obtained, confirming further the structural configurational Using enantioselective dynamic remarkable enantiomerization barriers determined for ortho-carbonates ortho-carbamates, values of up 27.6 34.6 kcal/mol (half-lives 227 days >84,000 years at 25 °C, respectively). DFT elucidates origin this large difference pointing toward preferred C-O or C-N bond cleavages in rate-determining step SN1-like mechanism.

Language: Английский

Citations

0