Herein, we reported the designed synthesis of three isostructural three-dimensional covalent organic frameworks (3D COFs) with -H, -Me,or-Fsubstituents,which have similar crystallinity and topology.T heir crystal structures were determined by continuous rotation electron diffraction (cRED), and all three 3D COFs were found to adopt af ivefold interpenetrated pts topology.M ore importantly,t he resolution of these cRED datasets reached up to 0.9-1.0 ,e nabling the localization of all non-hydrogen atomic positions in aC OF framework directly by 3D ED techniques for the first time.In addition, the precise control of the pore environments through the use of different functional groups led to different selectivities for CO 2 over N 2 .W eh ave thus confirmed that polycrystalline COFs can be definitely studied to the atomic level as other materials,a nd this study should also inspire the design and synthesis of 3D COFs with tailored pore environments for interesting applications.

Rational construction of covalent organic frameworks (COFs) with novel structures still remains a challenge. Herein, we report the designed synthesis of two COFs, 2D-BPTA-COF and 3D-BMTA-COF, starting from biphenyl-based precursors but with different groups at the ortho positions. Both COFs exhibited high crystallinity and large surface area, and interestingly, 2D-BPTA-COF crystallizes into 2D sheets with AB stacking mode while 3D-BMTA-COF adopts a 7-fold interpenetrated structure with pts topology. This structural difference could be ascribed to the introduction of methyl groups in the building blocks, as the dihedral angle of biphenyl rings in 2D-BPTA-COF is ∼0° while in 3D-BMTA-COF it is ∼60°. Therefore, it is possible to synthesize COFs with different structures by twisting building blocks from planar to tetrahedral with steric hindrance. We believe this result represents a general and straightforward way to expand the diversity of tetrahedral nodes for constructing 3D COFs in the future, and moreover, a new tetrahedral node for constructing 3D COFs is now available.

The construction of three-dimensional covalent organic frameworks (3D COFs) has proven to be very challenging, as their synthetic driving force mainly comes from the formation of covalent bonds. To facilitate the synthesis, rigid building blocks are always the first choice for designing 3D COFs. In principle, it should be very appealing to construct 3D COFs from flexible building blocks, but there are some obstacles blocking the development of such systems, especially for the designed synthesis and structure determination. Herein, we reported a novel highly crystalline 3D COF (FCOF-5) with flexible C–O single bonds in the building block backbone. By merging 17 continuous rotation electron diffraction data sets, we successfully determined the crystal structure of FCOF-5 to be a 6-fold interpenetrated pts topology. Interestingly, FCOF-5 is flexible and can undergo reversible expansion/contraction upon vapor adsorption/desorption, indicating a breathing motion. Moreover, a smart soft polymer composite film with FCOF-5 was fabricated, which can show a reversible vapor-triggered shape transformation. Therefore, 3D COFs constructed from flexible building blocks can exhibit interesting breathing behavior, and finally, a totally new type of soft porous crystals made of pure organic framework was announced.

The tuning of molecular switches in solid state toward stimuli-responsive materials has attracted more and more attention in recent years. Herein, we report a switchable three-dimensional covalent organic framework (3D COF), which can undergo a reversible transformation through a hydroquinone/quinone redox reaction while retaining the crystallinity and porosity. Our results clearly show that the switching process gradually happened through the COF framework, with an almost quantitative conversion yield. In addition, the redox-triggered transformation will form different functional groups on the pore surface and modify the shape of pore channel, which can result in tunable gas separation property. This study strongly demonstrates 3D COFs can provide robust platforms for efficient tuning of molecular switches in solid state. More importantly, switching of these moieties in 3D COFs can remarkably modify the internal pore environment, which will thus enable the resulting materials with interesting stimuli-responsive properties.

The activity of zinc is between that of magnesium and iron, and it has a suitable degradation rate and good biocompatibility. It has been regarded as a very promising biodegradable metal material for biomedicine. However, the insufficient mechanical properties of pure Zn limit its practical application in the field of orthopedic implants. In this paper, partially unzipped carbon nanotubes (PUCNTs) obtained by meridionally cutting multi-walled carbon nanotubes (MWCNTs) were used as reinforcements and combined with spark plasma sintering to prepare partially unzipped carbon nanotube reinforced Zn matrix composites. The effects of PUCNT addition on the microstructure and the mechanical properties of Zn matrix composites were investigated. The microstructure analysis showed the good interface bonding between PUCNTs and the Zn matrix. Additionally, the strength of PUCNTs/Zn composites showed a trend of increasing first and then decreasing with the PUCNT content increases. When the PUCNT content was 0.2 wt%, the tensile strength and yield strength of composites were about 78.4% and 64.4% higher than that of pure Zn, respectively, while maintaining a high elongation (62.6%).