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Nevertheless, the precise fabrication of PMC with tailored configurations, and a comprehensive understanding of their structure\u2010dependent property evolution, remains a formidable challenge. Herein, ligand engineering is employed to upgrade octanuclear Zn(II)\u2212siloxane\u2212PhPz clusters by grafting one more benzene ring onto azopyrazole ligand to form octanuclear Zn(II)\u2212siloxane\u2212BiPhPz clusters (OZSBPC). An integrated investigation combining kinetic analyses, in situ characterizations, and theoretical calculations reveals that the introduction of biphenyl moieties enlarges the intrinsic cavity to host more sulfur species, while the conjugation\u2010enhanced ligand framework facilitates more efficient electron transfer. Moreover, the enhanced nucleophilicity at nitrogen sites and the upshifted d\u2010band center synergistically strengthen the affinity toward polysulfides via \u03c0\u2212\u03c0 conjugation interactions. Consequently, the catalytic efficiency of OZSBPC undergoes a substantial enhancement, thereby enabling the assembled Ah\u2010class Li\u2212S pouch cell delivers a peak energy density of 504\u00a0Wh\u00a0kg<jats:sub>total<\/jats:sub><jats:sup>\u22121<\/jats:sup>, and sustains stable cycling at 429\u00a0Wh\u2009kg<jats:sub>total<\/jats:sub><jats:sup>\u22121<\/jats:sup> for 40 cycles. Moreover, stable operation over 150 cycles is achieved under \u221233\u00a0\u00b0C. Our study makes a breakthrough in precisely constructing PMC and in optimizing the performance via progressive structure upgrading, which made a landmark impact on lithium\u2212sulfur catalytic chemistry.<\/jats:p>","DOI":"10.1002\/anie.202516197","type":"journal-article","created":{"date-parts":[[2025,9,1]],"date-time":"2025-09-01T08:39:11Z","timestamp":1756715951000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Ligand Engineering\u2010Enhanced Catalytic Activity of Octanuclear Zn(II)\u2212Siloxane Clusters for Advanced Lithium\u2013Sulfur Batteries"],"prefix":"10.1002","volume":"64","author":[{"given":"Peng","family":"Wang","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tianyang","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Chemistry and 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