Negatively charged cavity engineering in metal-organic clusters for efficient photocatalytic C–P coupling

Clicks: 4
ID: 323412
2026
Article Quality & Performance Metrics
Overall Quality
Not rated
Combines reader engagement with the AI quality analysis. This article has not been analysed, so there is no overall score — reader engagement is measured and shown alongside.
AI Quality Assessment
Not analyzed
Readership in this journal
Steady

Ranked #173 of 284 articles by views in national science review

Most read Least read

Bar heights use a square-root scale. Only the 120 most-read articles are drawn; the journal has 284 in total.

Mint this article as an NFT
Not yet minted

Create a permanent, verifiable on-chain record of this article on the Scimatic Network. The NFT is held in your Journament account, and you can withdraw it to your own wallet at any time.

5 SUSD one-off · no wallet required
Abstract
Abstract Photocatalytic cross-dehydrogenative C–P coupling is a promising and environmentally sustainable method for the synthesis of important phosphides. The development of effective photocatalysts capable of regulating the formation and release of reactive intermediates is crucial for enhancing the efficiency and selectivity of target products; but it remains an extremely challenging task. In this study, we designed and scale-up synthesized an atomically precise Co4 cluster photocatalyst with a well-defined negatively charged cavity that can be used to effectively stabilize cationic intermediates during a one-pot sequential C–P coupling reaction. This unique Co4 cluster enables the homogeneous synthesis of hydroxylated N-aryl-tetrahydroisoquinoline (N-aryl-THIQ) products with a yield as high as 99% through photothermal catalytic oxidation of molecular oxygen (O2). Subsequently, these hydroxylated products act as stable reservoirs for reactive iminium cation intermediates, which effectively promote the heterogeneous nucleophilic substitution reaction of equimolar substrates under non-illumination conditions, achieving THIQ phosphides with an optimized yield exceeding 95%. More importantly, the employed photocatalytic strategy ensures the quantitative recovery of Co4 through recrystallization and enables the preparation of phosphide products over 10-gram via cyclic reactions. The experimental results (co-crystal structure of the Co4 unit with the intermediate product, UV-vis titration, XPS, and ESR characterizations) combined with DFT calculations disclosed that the negatively charged cavity in the Co4 cluster is instrumental in mediating reactive species through electrostatic and π-conjugated interactions, resulting in hydroxylation and nucleophilic substitution reactions. This work pioneers the negatively charged cavity engineering in catalysts, which efficiently mediates cationic intermediates, thereby enabling highly efficient photocatalytic C–P coupling reactions.
Reference Key
openalex_W7172309341 Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Dong-Ao Mao, Wei-Yang Li, He Wang, Bao-Kuan Chen, Jiang Liu, Yanfeng Bi, Ya-Qian Lan
Journal national science review
Year 2026
DOI
10.1093/nsr/nwag467
URL
Keywords Keywords not found

Citations

No citations found. To add a citation, contact the admin at info@scimatic.org

No comments yet. Be the first to comment on this article.