The structural diversity of three-dimensional (3D) covalent organic frameworks (COFs) are limited as there are only a few choices of building units with multiple symmetrically distributed connection sites. To date, 4 and 6-connected stereoscopic nodes with T d , D 3h , D 3d and C 3 symmetries have been mostly reported, delivering limited 3D topologies. We propose an efficient approach to expand the 3D COF repertoire by introducing a high-valency quadrangular prism (D 4h ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created. Low-dose electron microscopy allows the direct visualization of their 2-fold interpenetrated bcu networks. These 3D COFs are endowed with unique pore architectures and strong molecular binding sites, and exhibit excellent performance in separating C 2 H 2 /CO 2 and C 2 H 2 /CH 4 gas pairs. The introduction of highvalency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs.

No abstract

The structural diversity of three-dimensional (3D) covalent organic frameworks (COFs) are limited as there are only a few choices of building units with multiple symmetrically distributed connection sites. To date, 4 and 6-connected stereoscopic nodes with T d , D 3h , D 3d and C 3 symmetries have been mostly reported, delivering limited 3D topologies. We propose an efficient approach to expand the 3D COF repertoire by introducing a high-valency quadrangular prism (D 4h ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created. Low-dose electron microscopy allows the direct visualization of their 2-fold interpenetrated bcu networks. These 3D COFs are endowed with unique pore architectures and strong molecular binding sites, and exhibit excellent performance in separating C 2 H 2 /CO 2 and C 2 H 2 /CH 4 gas pairs. The introduction of highvalency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs.

The exceptional properties of two-dimensional covalent organic framework materials (2D-COFs), including their large π-conjugated structure at the molecular level and π−π multilayer stacking, have attracted interest for soft photothermal actuator applications. However, the conventional synthesis of COFs as microcrystalline powders limits their processing in water due to their limited dispersibility. Herein, we present a simple and environmentally friendly method to fabricate water-suspended COF inks by adjusting the surface potential of COF powders through adsorption of ionic species such as Na + and Cl − . This technique effectively prevents the accumulation and aggregation of COF powder, resulting in an aqueous COF ink that can be easily cast into homogeneous hybrid COF films by Mayer-rod coating. In addition, the resulting photothermal actuator exhibited a fast response time within 3 s at a curvature of 2.35 cm −1 in the near-infrared light. This facile and practical approach to fabricating water-based COFs ink represents a promising strategy for the development of practical applications of COFs in photothermal actuators.