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Covalent polymerization of organic molecules into crystalline one‐dimensional (1D) polymers is effective for achieving desired thermal, optical, and electrical properties, yet it remains a persistent synthetic challenge for their inherent tendency to adopt amorphous or semicrystalline phases. Here we report a strategy to synthesize crystalline 1D covalent organic frameworks (COFs) composing quasi‐conjugated chains with benzoxazine linkages via the one‐pot Mannich reaction. Through [4+2] and [2+2] type Mannich condensation reactions, we fabricated stoichiometric and sub‐stoichiometric 1D covalent polymeric chains, respectively, using doubly and singly linked benzoxazine rings. The validity of their crystal structures has been directly visualized through state‐of‐the‐art cryogenic low‐dose electron microscopy techniques. Post‐synthetic functionalizations of them with a chiral MacMillan catalyst produce crystalline organic photocatalysts that demonstrated excellent catalytic and recyclable performance in light‐driven asymmetric alkylation of aldehydes, affording up to 94 % enantiomeric excess [ABSTRACT FROM AUTHOR]

The alkylation of benzene with long chain α‐olefins is a crucial process in the production of fine chemicals, which requires the upgrading from traditional homogeneous catalysis to heterogeneous catalysis involving zeolites. However, the application of zeolite catalysts has been limited by their fast deactivation due to constrained diffusion resulting from the sole micropores. To address this challenge, a desilication and secondary‐crystallization strategy has been employed to fabricate hierarchically structured mesoporous Beta zeolites. The resultant mesoporous Beta zeolites demonstrate excellent catalytic activity and stability in the alkylation of benzene with 1‐dodecene, arising from the exposed acid sites and enhanced internal diffusion. Importantly, the internal diffusion limitations for these mesopore Beta zeolites are negligible, which significantly extends their lifetime and improves their regeneration performance. To achieve these benefits, the degree of mesopores must be deliberately controlled. Overall, this approach provides a promising solution for achieving efficient and environmentally friendly alkylation processes. [ABSTRACT FROM AUTHOR]

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 Td, D3h, D3d and C3 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 (D4h) 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 C2H2/CO2 and C2H2/CH4 gas pairs. The introduction of high‐valency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs. [ABSTRACT FROM AUTHOR]