RESUMEN
The assembly of cluster-based π-stacked porous supramolecular frameworks presents daunting challenges, including the design of suitable cluster building units, control of the sufficient C-H···π interactions, trade-off between structural dynamics and stability as well as understanding the resulting collective properties. Herein, we report a cluster-based C-H···π interaction-stacked porous supramolecular framework, namely, Cu12a-π, consisting of Cu12 nanocluster as a 6-connected node, which is further propagated to a dynamic porous supramolecular frameworks via dense intralayer C-H···π interactions, yielding permanent porosity. In addition, Cu12a-π can be transformed into cluster-based nonporous adaptive crystals (Cu12b-NACs) via ligand-exchange following a dissociation-reassembly mechanism. Moreover, Cu12a-π can efficiently remove 97.2% of iodine from saturated iodine aqueous solutions with a high uptake capacity of 2.96 g·g-1. These prospective results positioned at cluster-based porous supramolecular framework and enlighten follow-up researchers to design and synthesize such materials with better performance.
RESUMEN
The development of multi-functional materials as physical adsorbents for gas storage and dye adsorption is of utmost importance for ecological environment management. Ionic metal-organic frameworks (MOFs) with exchangeable counterions would easily be modified to enhance their performance. Herein, we report a novel {Zn5}-based MOF (SDU-CP-2) with the dimethylamine cation [(CH3)2NH2]+ in its crystal structure, which can be readily exchanged with Li+ ions and cationic dyes. Consequently, it exhibits high CO2 and C2H2 adsorption capacities as well as charge/size-selective adsorption of dye molecules. The adsorption of SDU-CP-2 toward cationic dyes was confirmed to be efficient in terms of recyclability and ion-exchange mechanisms. The column filler experiment and high water stability decisively supported its potential application in waste water treatment.
RESUMEN
Being isoelectronic with alkynes, iminoboranes with a polar B≡N triple bond have been exclusively investigated as a potent 1,2-dipole in synthetic chemistry. Herein, we disclose the unprecedented reactivity of aryliminoboranes via the BNCC π conjugation, namely hetero-enyne behavior. This allows for facile dearomative Diels-Alder-like reactions of aryliminoboranes with aldehydes. This cycloaddition features mild conditions, is catalyst-free, and has a broad substrate scope and good functional group tolerance. Kinetic and computational studies reveal its second-order reaction and concerted cyclization mechanism. This report unveils new synthetic application of iminoboranes beyond their classical reaction patterns.
