Porous organic polymers (POPs) are promising candidates for CO2 capture and conversion, yet the integration of direct air capture (DAC) and in situ conversion presents a fundamental challenge. Here, we report six novel water-dispersible cyclen-based POPs for efficient atmospheric CO2 capture and photoreduction. The resulting POPs ( POP-1 -6 ) exhibit exceptional aqueous-phase CO2 uptake (264-569 mg/g) with DAC capacities reaching 11-49 mg g-1 d-1 . When integrated with an iron porphyrin catalyst ( Fe-P ) and a ruthenium-based photosensitizer, these POPs enable efficient photocatalytic atmospheric CO2 -toCO conversion with rates of 1.4-4.5 mu mol g-1 h-1 and a yield up to 93 % in water. These findings provide valuable insights for the further exploration of POP materials for atmospheric CO2 capture and photoreduction. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

A relay catalytic system that integrates visible-light-enabled Ir-catalyzed asymmetric allylic etherification and dearomative [2 + 2] photocycloaddition has been developed. Unlike conventional ground-state asymmetric allylic dearomatization, this strategy takes advantage of the reactivity of triplet-state indoles. A diverse array of thermally disfavored cyclobutane-fused indolines was achieved in up to 92% yield with excellent diastereo- and enantioselectivities (up to >20:1 dr, >99% ee). Mechanistic studies, including control experiments and intermediate isolation, revealed that the irradiation of CHCl3 with blue LEDs generates HCl in situ, promoting the allylic substitution step. Kinetic analysis and same excess experiments indicated that photocycloaddition accelerates the preceding allylic substitution by consuming the allyl ether intermediate, thereby enabling the relay catalysis to achieve a synergistic 1 + 1 > 2 effect.

High-throughput virtual screening of catalysts in organic chemistry remains a grand challenge due to the prohibitive computational cost in exploring vast chemical spaces with quantum-chemical methods. Here, we develop the self-learning diffusion model coupled with potential energy surface exploration (SL-DM-PES) framework, which enables automated high-throughput virtual screening via templated organic reaction pathway construction. This self-learning (SL) framework integrates a general diffusion model (DM) for generating three-dimensional structures of reaction intermediates and transition states directly from two-dimensional molecular graphs, with generalized global neural network potential (GG-NN) calculations for rapid energy evaluation and structure optimization, namely the PES exploration. A high-order pair-reduced equivariant message passing neural network (HPNN-ET) is developed for DM, achieving high precision (RMSE <= 0.062="">

Regio- and stereoselective hydrocarbonylation of unactivated alkenes, including abundant light olefins produced on a large scale and a diverse range of other commercial and synthetic materials, remains a formidable challenge in fine-chemical synthesis. Here, we report a highly regio- and enantioselective alkoxycarbonylation of a range of unactivated terminal olefins with a variety of alcohols, including biologically relevant motifs, to afford valuable chiral esters in typically >95:5 enantiomeric ratios, >95:5 regioisomeric ratios, and >80% yields. Chiral alcohols bearing adjacent stereogenic centers can be transformed into either diastereomer of the products with >92:8 diastereomeric ratios and >80% yields. Central to this method is a palladium-bromide catalyst featuring a newly developed valley-shaped monophosphorus ligand, ValleyPhos. The crystal structure of the precatalyst (ValleyPhos)PdBr2 reveals that the chiral ligand forms a deep asymmetric pocket around the metal center, enabling precise enantiocontrol. The bromide ligand, in turn, is essential for achieving branched regioselectivity and suppressing deleterious chain-walking processes.

The variable oxidation states of nickel catalysts play an essential yet elusive role in reductive coupling reactions, wherein the rapid conversion of nickel species with different oxidation states into NiI has been recognized as a crucial factor in controlling the catalytic turnover and inhibiting side reactions. Beyond the popular strategies for reductive (re)generation of NiI species, spontaneous comproportionation of Ni0 and NiII species can form NiI during catalysis, which is an approach holding great promises yet still relatively underexplored in catalysis. Herein, we transform the intermolecular comproportionation into an entropically more favorable intramolecular pathway by taking advantage of a tetradentate nitrogen ligand (dppn), which effectively brings two catalytic Ni centers in close proximity. This strategy enables ready generation of catalytically active NiI species for reductive diarylation of dienes with aryl iodides using Mn as the terminal reductant. Mechanistic studies reveal that the dppn ligand facilitates the assembly of a dinickel complex, where one nickel acts as the catalytic site for oxidative addition and coupling while the other nickel functions as an electron reservoir. The intramolecular comproportionation pathway establishes a robust strategy for accessing the often fleeting and elusive NiI intermediates critical in forging C-C bonds in the reductive coupling reactions. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.