Modulating Supramolecular Chirality in Alanine Derived Assemblies by Multiple External Stimuli

Having control over the supramolecular chirality through multiexternal stimulators provides many possibilities in realizing functional chiral materials. Herein, the supramolecular chirality of nanotwists comprising PA centered with 1,4-phenyldicarboxamide bearing two l/d-helicogenic alanine motifs and achiral COOH at each terminus of the alanine arms is modulated by solvent, temperature, and ultrasound. The modulations are mainly due to the hydrogen bonds among gelators and solvent–gelator interactions, resulting in changes of the molecular arrangement and subsequent self-assembled nanostructures. Typically, the gel of PA in ethyl acetate prepared by ultrasonication method exhibits thixotropic property due to the participation of ethyl acetate in the self-assembly process, resulting in relatively flexible and tolerant networks. This study provides a simplistic way to control the handedness of chiral nanostructures and a rational design of the self-assembly system with multistimuli-responsive supramolecular chirality

Chiral Covalent Organic Cages: Structural Isomerism and Enantioselective Catalysis

Covalent organic cages are a prominent class of discrete porous architectures; however, their structural isomerism remains relatively unexplored. Here, we demonstrate the structural isomerism of chiral covalent organic cages that renders distinct enantioselective catalytic properties. Imine condensations of tetra-topic 5,10-di(3,5-diformylphenyl)-5,10-dihydrophenazine and ditopic 1,2-cyclohexanediamine produce two chiral [4 + 8] organic cage isomers with totally different topologies and geometries that depend on the orientations of four tetraaldehyde units with respect to each other. One isomer (PN-1) has an unprecedented Johnson-type J26 structure, whereas another (PN-2) adopts a tetragonal prismatic structure. After the reduction of the imine linkages, the cages are transformed into two amine bond-linked isomers PN-1R and PN-2R. After binding to Ni(II) ions, both can serve as efficient catalysts for asymmetric Michael additions, whereas PN-2R affords obviously higher enantioselectivity and reactivity than PN-1R presumably because of its large cavity and open windows that can concentrate reactants for the reactions. Density-functional theory (DFT) calculations further confirm that the enantioselective catalytic performance varies depending on the isomer

Data.xlsx

This file includes monthly or phenological-periodic mean values of litterfall, leaf area index, water-use efficiency, air temperature and soil water content in Southwest China rubber plantations at four stand ages and planting densities