A set of silver(I) 3,5-bis(trifluoromethyl) pyrazolate adducts with 1,10-phenanthroline (L²), 2,9-dimethyl-1,10-phenanthroline (neocuproine, L³) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, L⁴) was synthesized starting from trimeric silver pyrazolate Ag₃Pz₃. Reactions with sterically hindered L³ and L⁴ cause the destruction of the original trimeric core, yielding a dinuclear Ag₂Pz₂ cycle with an unprecedented chair configuration for L³, while bathocuproine L⁴ leads to the drastic rearrangement of the silver pyrazolate core into cationic Ag(L⁴)₂ and anionic Ag₅Pz₆ subunits. All complexes obtained exhibit phosphorescence in the solid state. Time-dependent density functional theory calculations demonstrate their different possible emission processes, explaining their emission behavior as well as their lifetimes.