1：Experimental Design and Method Selection:

The study involved the synthesis of manganese-doped fluorozirconate glasses with varying degrees of chlorine substitution for fluorine. Luminescence and EPR spectra were measured to analyze the effects of chlorine substitution.

2：Sample Selection and Data Sources:

ZBLAN fluorozirconate glasses doped with 0.1–2 mol % MnO2 were prepared. Chlorine-containing ZBLAN?Cl? glasses were prepared through partial or complete BaCl2 substitutions for BaF

3：1–2 mol % MnO2 were prepared. Chlorine-containing ZBLAN?Cl? glasses were prepared through partial or complete BaCl2 substitutions for BaFList of Experimental Equipment and Materials:

2. 3. List of Experimental Equipment and Materials: ZrF4 (Sigma-Aldrich, 99.9%), BaF2 (Lanhit Ltd., 99.998%), LaF3 (Lanhit Ltd., 99.99%), AlF3 (Sigma-Aldrich, 99.9%), NaF (Merck, 99.99%), MnO2 (Lanhit Ltd., 99.9%), and BaCl2 (Sigma-Aldrich, 99.9%).

4：9%), BaF2 (Lanhit Ltd., 998%), LaF3 (Lanhit Ltd., 99%), AlF3 (Sigma-Aldrich, 9%), NaF (Merck, 99%), MnO2 (Lanhit Ltd., 9%), and BaCl2 (Sigma-Aldrich, 9%). Experimental Procedures and Operational Workflow:

4. Experimental Procedures and Operational Workflow: Glass samples were prepared in glassy carbon crucibles enclosed in an argon-filled quartz reactor, melted between 900 and 950°C, and cooled in flowing argon at room temperature.

5：Data Analysis Methods:

Luminescence spectra were taken on an SDL-1 spectrometer, and EPR spectra were measured on a Bruker ER 200 D spectrometer.