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The structure and optical properties of B2O3-Al2O3-Na2O glasses were investigated in this work as a function of B2O3 concentration.With increase of B2O3 content,the emission intensity of doped rare earth ions Sm3+,Dy3+ and Tb3+ was enhanced significantly.While in the metal silver ions doped samples,the luminescence of single silver ions decreased and the silver clusters emission was enhanced.Structure measurements were made by the Raman spectra,FTIR spectra and NMR spectra for the above optical phenomenon.The results indicated that the glass structure experienced the transformation of [BO4] units to [BO3] units.The highly polymerized structure units composed by the [BO4] were broken down to the [BO3] mainly formed lowly poiymerized structure units with increase of B2O3 proportion.During the decomposition process,the rare earth ions were well dispersed in the matrix leading to the decrease of the concentration quenching effect and thus increased the luminescence efficiency.For the metal silver ions,the silver state was promoted to aggregate to the silver clusters from the singly silver ions.It is demonstrated the controllable ability of glasses structure on the optical and chemical properties of doped ions.