ABSTRACT Photocatalytic oxidation mediated by reactive oxygen species (ROS) provides an effective platform for a wide range of important chemical transformations. However, conventional oxygen‐vacancy engineering strategy, while enhancing O 2 activation, often hampers subsequent ROS evolution due to overly strong adsorption, thereby limiting oxidation kinetics. Here, we demonstrate that asymmetric vacancies in ZnGa 2 O 4 , characterized by a Zn Td −O v −Ga Oh configuration, can overcome this intrinsic limitation by synergistically coupling O 2 activation with efficient ROS evolution. Specifically, the dynamic Ga Oh site preferentially promotes O 2 adsorption and activation, whereas the Zn Td site interacts weakly with oxygen‐derived species, facilitating ROS release and vacancy replenishment, thereby achieving an optimal balance between these critical steps. Consequently, Ag/ZnGa 2 O 4 delivers the highest turnover number (TON) reported to date among Ag‐based catalysts for the photocatalytic oxidative coupling of methane via a ROS‐mediated pathway. The general effectiveness of this asymmetric‐vacancy strategy is further validated in other representative photocatalytic reactions, including hydrogen peroxide production and the oxidative coupling of benzyl alcohol.

The cover illustrates how spiral structures at different length scales give rise to chiral light emission. Length-controlled molecular spirals of tetraazahelicenes inherit this motif, and an increase in helix length leads to more coherently organized chiral π-systems, resulting in enhanced circularly polarized luminescence. The swirling light patterns visualize the progression from natural spirals to molecular helicity and finally to circularly polarized light, highlighting a design principle for advanced CPL materials based on molecular length control. More information in the Research Article (e24463), Takashi Otani, Kohei Ueda, Takanori Shibata, and co-workers.

Nanocluster-stabilized sulfur-based superradical is reported by Zhikun Wu and co-workers in the Research Article (e17738). The superradical Au64(CPT)31S· was obtained through the homolytic cleavage of the thiolate S─C bond in the Au64(CPT)32 nanocluster precursor by radiative or solvent-induced methods. It can initiate the polymerization of pentaerythritol triacrylate in 3D printing despite its ultrastability. In addition, the superradical and its precursor exhibit NIR-II photoluminescence and high photothermal conversion efficiencies.

In the Research Article (e23981), Lin Cheng, Liping Cao, and co-workers designed and synthesized a crown-ether-functionalized tetraphenylethene-based cationic cage. This multi-cavity molecular cage establishes a multi-domain cooperative hydrophobic microenvironment that enhances hydrogen bonding among sequence-diverse dinucleotides in aqueous conditions. The study provides valuable insights into the sequence-dependent diversity of base hydrogen-bonding structures within artificial systems, potentially uncovering patterns that may also be present in nature.

The cover illustrates dual n-type and p-type redox pathways in quinone-based bipolar cathodes. Carbonyl backbones and p-type functional groups cooperate to store both Li cations and PF6 anions, while the magnified LUMO anti-bonding orbitals activate the p-type process. This molecular design concept enables high-voltage, high-capacity organic cathodes for next-generation batteries. More in the Research Article (e21979), Ki Chul Kim and co-workers.