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Herein, an ingenious approach is presented for constructing a phosphorescent SQDs\u2010based system (\u03c0\u2010SQDs\u2010MA) by integrating \u03c0\u2010conjugated units with covalent confinement in a metaboric acid (MA) matrix. Remarkably, \u03c0\u2010SQDs\u2010MA exhibits intense intrinsic green RTP with a high efficiency of 19.61% and demonstrates exceptional long\u2010term stability, along with outstanding resistance to quenching by solvents, light, oxygen, pH fluctuations, and external pressure. Detailed analyses revealed that incorporating \u03c0\u2010conjugated units enhances the generation of effective triplet states with mixed (n, \u03c0*) and (\u03c0, \u03c0*) electron configurations, while covalent bonding between \u03c0\u2010SQDs and MA forms a highly rigid, densely interconnected network that activates RTP by confining triplet excitons and suppressing nonradiative decay. Leveraging its phosphorescent photodynamic antibacterial therapy and inherent antibacterial properties, \u03c0\u2010SQDs\u2010MA exhibited potent synergistic bactericidal effects, achieving near\u2010complete inactivation of\n                    <jats:italic>Staphylococcus aureus<\/jats:italic>\n                    and\n                    <jats:italic>Escherichia coli<\/jats:italic>\n                    within 2\u00a0min, markedly outperforming existing sterilization materials and conventional antibiotics. Additionally, multicolor afterglow is demonstrated via triplet\u2010to\u2010singlet energy transfer, highlighting their potential in displays and dynamic multilevel encryption.\n                  <\/jats:p>","DOI":"10.1002\/smll.202506316","type":"journal-article","created":{"date-parts":[[2025,8,19]],"date-time":"2025-08-19T13:00:20Z","timestamp":1755608420000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Intrinsic Bright and Robust Phosphorescence in Sulfur Quantum Dots Enabled by \u03c0\u2010Conjugation Engineering and Covalent Matrix Anchoring"],"prefix":"10.1002","volume":"21","author":[{"given":"Heng","family":"Zhou","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering Qilu University of Technology (Shandong Academy of Sciences)  Jinan 250353 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