Precise control from a metal-free catalyst: Polymerization can be a rather dangerous free for all, with molecules joining randomly in chains at a chaotic pace. One of modern chemistry's great accomplishments has been the development of methods to assemble polymers in steady, orderly steps. However, order comes at a price, and often it's the need for metal catalysts that are hard to remove from the plastic product. Theriot et al. used theory to guide the design of a metal-free light-activated catalyst that offers precise control in atom transfer radical polymerization, alleviating concerns about residual metal contamination (see the Perspective by Shanmugam and Boyer). Science , this issue p. 1082 ; see also p. 1053

Macrocycle-to-framework strategy was explored to prepare covalent organic frameworks (COFs) using shape-persistent macrocycles as multitopic building blocks. We demonstrate well-ordered mesoporous 2D COFs (AEM–COF-1 and AEM–COF-2) can be constructed from tritopic arylene-ethynylene macrocycles, which determine the topology and modulate the porosity of the materials. According to PXRD analysis and computer modelling study, these COFs adopt the fully eclipsed AA stacking mode with large accessible pore sizes of 34 or 39 Å, which are in good agreement with the values calculated by NLDFT modelling of gas adsorption isotherms. The pore size of COFs can be effectively expanded by using larger size of the macrocycles. Provided a plethora of polygonal shape-persistent macrocycles with various size, shape and internal cavity, macrocycle-to-framework strategy opens up a promising approach to expand the structural diversity of COFs and build hierarchical pore structures within the framework.

We present the development of a conjugated porous Co( ii ) porphyrinylene–ethynylene framework as an efficient oxygen reduction catalyst through alkyne metathesis polymerization.