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In this study, a series of Ag\n                    <jats:sub>6<\/jats:sub>\n                    L\n                    <jats:sub>6<\/jats:sub>\n                    clusters, Ag\n                    <jats:sub>6<\/jats:sub>\n                    (PPT)\n                    <jats:sub>6<\/jats:sub>\n                    , Ag\n                    <jats:sub>6<\/jats:sub>\n                    (FPPT)\n                    <jats:sub>6<\/jats:sub>\n                    , and Ag\n                    <jats:sub>6<\/jats:sub>\n                    (2FPPT)\n                    <jats:sub>6<\/jats:sub>\n                    , were constructed using stepwise fluorinated ligands. All three clusters feature a slightly distorted octahedral Ag\n                    <jats:sub>6<\/jats:sub>\n                    core, while fluorination reorganizes intercluster interactions through C\u2500H\u00b7\u00b7\u00b7F contacts, leading to more regular and compact crystal packing with enhanced lattice rigidity. Photophysical studies reveal that fluorination modulates the emission properties and increases the photoluminescence quantum yield from 35.66% to 98.67%. Theoretical simulations elucidate that fluorination localizes the lowest charge\u2010transfer excited states, simplifies the composition of excited states, and shifts the emissive states from greater metal\u2010centered character toward increased ligand participation, thereby favoring radiative decay and suppressing excited\u2010state absorption. Consequently, both absorption\u2010 and scattering\u2010related losses are effectively suppressed, resulting in a substantial decrease in optical loss coefficients from 0.04164 to 0.00365\u00a0dB \u00b5m\n                    <jats:sup>\u22121<\/jats:sup>\n                    . Ligand fluorination emerges as a robust approach to achieving organized molecular packing, bolstered lattice rigidity, and refined excited\u2010state configurations, paving the way for high\u2010efficiency, low\u2010loss cluster\u2010based optical waveguides.\n                  <\/jats:p>","DOI":"10.1002\/anie.5830758","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T10:59:27Z","timestamp":1789469967000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Integrating Rigidity and Regular Packing in Ag\n                    <sub>6<\/sub>\n                    Clusters via Ligand Fluorination: Toward High\u2010Efficiency Low\u2010Loss Optical Waveguiding"],"prefix":"10.1002","volume":"65","author":[{"given":"Yi\u2010Peng","family":"Zhang","sequence":"first","affiliation":[{"name":"Key Laboratory of Functional Inorganic Material Chemistry Ministry of Education School of Chemistry and Materials Heilongjiang University  Harbin P. 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