Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films.

Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest SBET of 1 151 m2 g-1) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m-2 h-1 bar-1.

Selective Molecular Sieving in Self-Standing Porous Covalent-Organic-Framework Membranes.

Self-standing, flexible, continuous, and crack-free covalent-organic-framework membranes (COMs) are fabricated via a simple, scalable, and highly cost-effective methodology. The COMs show long-term durability, recyclability, and retain their structural integrity in water, organic solvents, and mineral acids. COMs are successfully used in challenging separation applications and recovery of valuable active pharmaceutical ingredients from organic solvents.

Aromatic C-nitrosation by a copper(II)-nitrosyl complex.

Copper(II) complex of 4-amino-3-hydroxy-1-sulphonic acid was synthesized and characterized. Upon addition of nitric oxide, the copper(II) center of the complex in methanol was found to undergo reduction through an unstable copper(II)-nitrosyl intermediate. The formation of the intermediate was confirmed by UV-visible and FT-IR spectroscopy. The reduction of the copper(II) center was accompanied with a simultaneous C-nitrosation of the aromatic ring of the ligand. The C-nitrosation product was isolated and characterized by various spectroscopic analyses.