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.

Direct observation of the surface-enhanced Raman scattering (SERS) of molecules adsorbed on nano-sized zirconia (ZrO 2 ) substrates was first reported without the need for the addition of metal particles. It was found that ZrO 2 nanoparticles can exhibit unprecedented Raman signal enhancements on the order of 10 3 for the probe molecule 4-mercaptobenzoic acid (4-MBA). The dramatic effect of the calcination temperature on the ZrO 2 nanoparticles was also investigated. The ZrO 2 nanoparticles with the particle diameter of 10.5 nm, which were prepared by calcination at a temperature of 500°C, have the highest SERS activity. A comparison between the experimental and calculation results indicates that charge transfer (CT) effects dominate the surface enhancement. The plentiful surface state of ZrO 2 active substrate that is beneficial to CT resonance occurs between molecules and ZrO 2 to produce a SERS effect. The CT process depends, to a large extent, on the intrinsic properties of the modifying molecules and the surface properties of the ZrO 2 . This is a new SERS phenomenon for ZrO 2 that will expand the application of ZrO 2 to microanalysis and is beneficial for studying the basic properties of both ZrO 2 and SERS.

There are enormous yet largely underexplored exotic phenomena and properties emerging from interfaces constructed by diverse types of components that may differ in composition, shape, or crystal structure. It remains poorly understood the unique properties a coherent interface between crystalline and amorphous materials may evoke, and there lacks a general strategy to fabricate such interfaces. It is demonstrated that by topotactic partial oxidation heterostructures composed of coherently registered crystalline and amorphous materials can be constructed. As a proof‐of‐concept study, heterostructures consisting of crystalline P3N5 and amorphous P3N5Ox can be synthesized by creating amorphous P3N5Ox from crystalline P3N5 without interrupting the covalent bonding across the coherent interface. The heterostructure is dictated by nanometer‐sized short‐range‐ordered P3N5 domains enclosed by amorphous P3N5Ox matrix, which entails simultaneously fast charge transfer across the interface and bicomponent synergistic effect in catalysis. Such a P3N5/P3N5Ox heterostructure attains an optimal adsorption energy for *OOH intermediates and exhibits superior electrocatalytic performance toward H2O2 production by adopting a selectivity of 96.68% at 0.4 VRHE and a production rate of 321.5 mmol h−1 gcatalyst−1 at −0.3 VRHE. The current study provides new insights into the synthetic strategy, chemical structure, and catalytic property of a sub‐nanometer coherent interface formed between crystalline and amorphous materials.

The integration of mechanically interlocked molecules (MIMs) into purely organic crystalline materials is expected to produce materials with properties that are not accessible using more classic approaches. To date, this integration has proved elusive. We present a dative boron–nitrogen bond-driven self-assembly strategy that allows for the preparation of polyrotaxane crystals. The polyrotaxane nature of the crystalline material was confirmed by both single-crystal x-ray diffraction analysis and cryogenic high-resolution low-dose transmission electron microscopy. Enhanced softness and greater elasticity are seen for the polyrotaxane crystals than for nonrotaxane polymer controls. This finding is rationalized in terms of the synergetic microscopic motion of the rotaxane subunits. The present work thus highlights the benefits of integrating MIMs into crystalline materials.

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.