Restriction of Molecular Rotors in Ultrathin Two-Dimensional Covalent Organic Framework Nanosheets for Sensing Signal Amplification

Abstract

Covalent organic frameworks (COFs) have emerged as promising crystalline porous materials with well-defined structures, high porosity, tunable topology, and functionalities suitable for various applications. However, studies of few-layered ultrathin two-dimensional (2D) COF nanosheets, which may lead to unprecedented properties and applications, are still limited. Herein, we report the targeted synthesis of three azine-linked and imine-linked 2D COFs named NUS 30–32 using monomers containing aggregation-induced emission (AIE) rotor-active tetraphenylethylene (TPE) moieties, affording micro- and meso-dual pores in NUS-30 and NUS-32 and triple pores in NUS-31. For the first time, we demonstrate that these isostructural bulk COF powders can be exfoliated into ultrathin 2D nanosheets (2–4 nm thickness) by a temperature-swing gas exfoliation approach. Compared with TPE monomers and COF model compounds, the AIE characteristic of NUS 30–32 nanosheets is distinctly suppressed because of the covalent restriction o...