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For photoluminescence (PL) properties of Mn
2+
in glass–ceramics are highly dependent on the concentration of Mn
2+
, we experimentally observed the change of Mn
2+
structures from isolated Mn
2+
ion as a tetrahedron, octahedron to Mn
2+
-Mn
2+
dimer in B-P-Zn-K based glass–ceramics with characteristic PL peaks locating at 504 nm, 600 nm, and 660 nm, respectively. Spectral results reveal that condensed Mn
2+
would lead to redshift of PL emission and reduced Luminous intensity caused by concentration quenching, however, with increasing Mn
2+
content, shift of Mn
2+
structure is the determining factor for PL redshift. Moreover, compared with tetrahedral and octahedral Mn
2+
, Mn
2+
-Mn
2+
dimer exhibits highly enhanced PL emission and shortened life span which reveal that transitions of Mn
2+
-Mn
2+
dimer are far more efficient than those transitions in tetrahedral and octahedral Mn
2+
. This enables tuning of color and efficiency of PL emission for Mn-doped glass–ceramics via a simple method.
Graphical abstract