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However, accompanying steric hindrance effects can significantly impede the reaction progress, presenting a critical dilemma in synthetic design. Herein, a vacancy-constrained strategy was proposed for breaking steric hindrance restriction by realizing the deep-level delocalization of a catalyst with compressed metal bonds. In detail, the delocalized deep-level orbit exhibits strong penetrating capability that overcomes the steric hindrance effect of large functional groups by enhancing the charge-transfer process between the active sites and substrates. By taking bismuth atoms supported on defective CeO2 as an example, an \u2018O4-Bi-Bi-O4\u2019 ensemble was constructed by confining two adjacent Bi atoms in the vacancy of CeO2 nanosheets, where the Bi\u2013Bi bond was strongly constrained from 3.10 to 3.05\u00a0\u00c5. Such a functional Bi2\/CeO2 catalyst exhibits enhanced photocatalytic efficiency in overcoming the steric hindrance from large functional groups, which is three times and two times higher than that of Bi single-atom catalyst and Bi cluster catalyst, respectively. This work proposes an applicable way of overcoming steric hindrance effects in the synthesis of high-value-added chemicals.<\/jats:p>","DOI":"10.1093\/nsr\/nwag388","type":"journal-article","created":{"date-parts":[[2026,7,6]],"date-time":"2026-07-06T15:52:32Z","timestamp":1783353152000},"source":"Crossref","is-referenced-by-count":0,"title":["Breaking steric hindrance restriction: compressed metal bonds realizing deep-level orbital delocalization"],"prefix":"10.1093","volume":"13","author":[{"given":"Hanghao","family":"Ying","sequence":"first","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liuxin","family":"Xu","sequence":"additional","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xia","family":"Zhong","sequence":"additional","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yi","family":"Liu","sequence":"additional","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaodong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yi","family":"Xie","sequence":"additional","affiliation":[{"name":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026 ,","place":["China"]},{"name":"State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China , Hefei 230026 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"286","published-online":{"date-parts":[[2026,7,6]]},"reference":[{"key":"2026092510223654500_bib1","doi-asserted-by":"publisher","first-page":"485","DOI":"10.1038\/s41565-022-01087-3","article-title":"A. 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