Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages

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

Published: March 2, 2025

The development of new chiral building blocks for constructing complex architectures, such as macrocycles and cages, is both crucial challenging. Although concave-shaped calixarenes have been established versatile the synthesis cage compounds, there are no reports on cages constructed from calix[4]arene derivatives. Herein, we present a straightforward effective method gram-scale member macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As proof concept, functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via Duff reaction to construct porous organic (CPOCs) using polyamine synthons. Specifically, employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine tris(4-aminophenyl)amine, assemble with PC[4]ACHO resulting in [2 + 4] lantern-shaped [6 8] truncated octahedral CPOCs, respectively. These structures unambiguously characterized by single-crystal X-ray diffraction circular dichroism (CD) spectroscopy. Notably, CPOCs exhibit internal diameters approximately 3.1 nm, cavity volume around 5300 Å3, high specific surface areas up 1300 m2 g-1 after desolvation, making them among largest reported. Additionally, investigations their sensing performance demonstrate that PC[4]A-based enable enantioselective recognition amino acids This work strongly suggests PC[4]A can serve an excellent block rational design materials practical applications.

Language: Английский

Spherical Amides with C3 Symmetry: Improved Synthetic Approach and Structural/Optical Analysis

Molecules, Journal Year: 2025, Volume and Issue: 30(5), P. 1074 - 1074

Published: Feb. 26, 2025

A spherical amide with C3 symmetry was synthesized by a one-step cyclization reaction using triphenylphosphine and hexachloroethane as coupling reagents. This method enabled synthesis of N-benzyl N-allyl derivatives, which could not be obtained the previously reported method. The optical resolution each compound measured, their electronic circular dichroism spectra revealed that they were mirror images. high structural resulted in higher Δε (molar absorption difference against right or left polarization: εL - εR value compared to another isomer previously. absolute structure enantiopure crystal derivative determined Flack parameter X-ray crystallographic analysis.

Language: Английский

One‐step Macrocycle‐to‐Macrocycle Conversion Towards Two New Macrocyclic Arenes with Different Structures and Properties

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

Two new macrocyclic arenes H1 and H2 were conveniently synthesized by the one-step reaction of carboxylic acid substituted octopus[3]arene. It was found that composed three ethenoanthracene subunits with a rigid hexagonal structure contained two one anthracene subunit house-shaped structure. Among them, exhibited strong blue fluorescence due to existence an subunit. Moreover, both showed large electron-rich cavities, which enable them effectively complex different nitrogen-containing heterocyclic salt guests in solution solid state. further stronger complexation towards tested than probably charge-transfer interactions between guests.

Language: Английский