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Direct arylation provides pathways to enhance the solution processability of particles and manipulate the photophysical and electronic properties of SiNCs. Unfortunately, existing methods employed to prepare aryl\u2010functionalized SiNCs are based on organometallic coupling or transition\u2010metal\u2010catalyzed strategies, which require metal\u2010based reagents for preactivation or the precursors and complicated post\u2010treatment processes for product purification. Herein, we demonstrate a metal\u2010free method that directly functionalizes SiNCs with aryl\u2010based ligands. We design a series of benzyne derivatives formed from the thermal cyclization of predesigned alkynes, allowing efficient arylation on hydride\u2010terminated silicon surfaces under mild conditions. These aryl\u2010functionalized SiNCs exhibit strong blue emissions with nanosecond\u2010scaled decay, suggesting the formation of a new radiative recombination channel on SiNC surfaces.<\/jats:p>","DOI":"10.1002\/anie.202304056","type":"journal-article","created":{"date-parts":[[2023,4,26]],"date-time":"2023-04-26T07:30:21Z","timestamp":1682494221000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Direct Arylation of Silicon Nanocrystals with Hexadehydro\u2010Diels\u2013Alder\u2010Derived Benzynes"],"prefix":"10.1002","volume":"62","author":[{"given":"Ming","family":"Lai","sequence":"first","affiliation":[{"name":"MOE Laboratory of Bioinorganic and Synthetic Chemistry Lehn Institute of Functional Materials School of Chemistry Sun Yat-sen University  Guangzhou Guangdong 510275 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