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Here, inspired by the characteristic topologies of molecular compounds, we introduce \u201cpacking-structure engineering\u201d via a ligand solubility-matched microemulsion-confined co-assembly strategy to fabricate three typical mesoscopic packing-topology structural systems from Au nanoparticles and CdSe\/CdS nanorods: metal-isolated-by-semiconductor-type, metal-interlaced-with-semiconductor-type, and semiconductor-isolated-by-metal-type. We demonstrate that packing topology acts as a fundamental independent order parameter\u2500analogous to molecular connectivity topologies\u2500fundamentally regulating intrinsic electron dynamics. Specifically, the metal-isolated-by-semiconductor configuration enables a transition from picosecond incoherent hot-electron transfer to instantaneous coherent plasmon-induced interfacial charge-transfer transition, comparable to contacting heterostructures. This behavior may arise from unique collective coupling modes and interparticle field enhancements. This offers a pathway for minimizing thermalization losses in the plasmonic donor. Extendable to diverse systems, it can unlock emergent optoelectronic properties and high-performance materials for applications in solar cells, photodetectors, photocatalysis, and sensing.<\/jats:p>","DOI":"10.1021\/jacs.6c17293","type":"journal-article","created":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T16:02:09Z","timestamp":1791475329000},"page":"45125-45135","source":"Crossref","is-referenced-by-count":0,"title":["Nanoparticle\nPacking-Dependent Charge Transfer Dynamics\nin Colloidal Binary Superparticles"],"prefix":"10.1021","volume":"148","author":[{"given":"Cancan","family":"Li","sequence":"first","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]},{"name":"Chinese Academy of Sciences (CAS) , , ,","place":["Beijing, P. R. China, 100190"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, P. R. China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3613-7271","authenticated-orcid":true,"given":"Shuai","family":"Yue","sequence":"additional","affiliation":[{"name":"National Center for Nanoscience and Technology , ,","place":["Beijing, P. R. China, 100190"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lindong","family":"Ma","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhenjie","family":"Xue","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haochen","family":"Ye","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Deyu","family":"Bao","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shan","family":"Zhu","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiaxing","family":"Liu","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8260-469X","authenticated-orcid":true,"given":"Xiao","family":"Li","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7662-7171","authenticated-orcid":true,"given":"Xinfeng","family":"Liu","sequence":"additional","affiliation":[{"name":"National Center for Nanoscience and Technology , ,","place":["Beijing, P. R. China, 100190"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5965-6520","authenticated-orcid":true,"given":"Tie","family":"Wang","sequence":"additional","affiliation":[{"name":"Tianjin University of Technology , , ,","place":["Tianjin, P. R. China, 300384"]},{"name":"Chinese Academy of Sciences (CAS) , , ,","place":["Beijing, P. R. China, 100190"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, P. R. China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,8]]},"reference":[{"issue":"6319","key":"2026102111072336000_cit1","doi-asserted-by":"publisher","first-page":"1580","DOI":"10.1126\/science.aak9750","article-title":"Emergence of hierarchical\nstructural complexities in nanoparticles\nand their assembly","volume":"354","author":"Zeng","year":"2016","journal-title":"Science"},{"issue":"5797","key":"2026102111072336000_cit2","doi-asserted-by":"publisher","first-page":"274","DOI":"10.1126\/science.1128045","article-title":"Self-Assembly\nof CdTe Nanocrystals into Free-Floating Sheets","volume":"314","author":"Tang","year":"2006","journal-title":"Science"},{"issue":"5","key":"2026102111072336000_cit3","doi-asserted-by":"publisher","first-page":"4976","DOI":"10.1021\/acs.chemrev.1c00482","article-title":"Colloidal Self-Assembly Approaches to Smart Nanostructured\nMaterials","volume":"122","author":"Li","year":"2022","journal-title":"Chem. 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Soc."},{"issue":"21","key":"2026102111072336000_cit24","doi-asserted-by":"publisher","first-page":"7708","DOI":"10.1021\/ja5023893","article-title":"Hole Removal Rate Limits Photodriven\nH2 Generation Efficiency in\nCdS-Pt and CdSe\/CdS-Pt Semiconductor Nanorod\u2013Metal Tip Heterostructures","volume":"136","author":"Wu","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"6248","key":"2026102111072336000_cit25","doi-asserted-by":"publisher","first-page":"632","DOI":"10.1126\/science.aac5443","article-title":"Efficient hot-electron\ntransfer by a plasmon-induced interfacial charge-transfer transition","volume":"349","author":"Wu","year":"2015","journal-title":"Science"},{"issue":"7","key":"2026102111072336000_cit26","doi-asserted-by":"publisher","first-page":"3790","DOI":"10.1021\/acs.chemrev.2c00770","article-title":"Rich Landscape\nof Colloidal Semiconductor\u2013Metal\nHybrid Nanostructures: Synthesis, Synergetic Characteristics, and\nEmerging Applications","volume":"123","author":"Ben-Shahar","year":"2023","journal-title":"Chem. 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Bull."},{"issue":"3","key":"2026102111072336000_cit39","doi-asserted-by":"publisher","first-page":"2207555","DOI":"10.1002\/adma.202207555","article-title":"Ultralong Lifetime of Plasmon-Excited Electrons\nRealized in Nonepitaxial\/Epitaxial\nAu@CdS\/CsPbBr3 Triple-Heteronanocrystals","volume":"35","author":"Wan","year":"2023","journal-title":"Adv. Mater."},{"issue":"11","key":"2026102111072336000_cit40","doi-asserted-by":"publisher","first-page":"5255","DOI":"10.1021\/nl402730m","article-title":"Plasmon-Induced\nHot Electron Transfer from the Au Tip to CdS Rod in CdS-Au Nanoheterostructures","volume":"13","author":"Wu","year":"2013","journal-title":"Nano Lett."},{"issue":"10","key":"2026102111072336000_cit41","doi-asserted-by":"publisher","first-page":"732","DOI":"10.1038\/nnano.2010.176","article-title":"Optical rectification\nand field enhancement in a plasmonic nanogap","volume":"5","author":"Ward","year":"2010","journal-title":"Nat. Nanotechnol."},{"issue":"12","key":"2026102111072336000_cit42","doi-asserted-by":"publisher","first-page":"1013","DOI":"10.1038\/nnano.2015.247","article-title":"Charge transport\nin strongly coupled quantum dot solids","volume":"10","author":"Kagan","year":"2015","journal-title":"Nat.\nNanotechnol."},{"issue":"6302","key":"2026102111072336000_cit43","doi-asserted-by":"publisher","first-page":"aac5523","DOI":"10.1126\/science.aac5523","article-title":"Building devices\nfrom colloidal quantum dots","volume":"353","author":"Kagan","year":"2016","journal-title":"Science"},{"issue":"6","key":"2026102111072336000_cit44","doi-asserted-by":"publisher","first-page":"2927","DOI":"10.1021\/acs.chemrev.7b00430","article-title":"Surface-Plasmon-Driven\nHot Electron Photochemistry","volume":"118","author":"Zhang","year":"2018","journal-title":"Chem. Rev."},{"issue":"14","key":"2026102111072336000_cit45","doi-asserted-by":"publisher","first-page":"8597","DOI":"10.1021\/acs.chemrev.4c00165","article-title":"Plasmon-Induced Hot Electrons in\nNanostructured Materials: Generation, Collection, and Application\nto Photochemistry","volume":"124","author":"Zhou","year":"2024","journal-title":"Chem. Rev."},{"issue":"17","key":"2026102111072336000_cit46","doi-asserted-by":"publisher","first-page":"6084","DOI":"10.1021\/ja9015183","article-title":"Cylindrical Superparticles from Semiconductor\nNanorods","volume":"131","author":"Zhuang","year":"2009","journal-title":"J. Am. Chem. Soc."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c17293","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/45125\/68790815\/jacs.6c17293.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/45125\/68790815\/jacs.6c17293.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:30:11Z","timestamp":1792596611000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/41\/45125\/5447184\/Nanoparticle-Packing-Dependent-Charge-Transfer"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,8]]},"references-count":46,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,8]]},"published-print":{"date-parts":[[2026,10,21]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c17293","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,8]]}}}