Luminescence enhancement and tuning via multiple cooperative supramolecular interactions in an ion-paired multinuclear complex

[(3,5-(CF3)2Pz)(AgL)2]+[Ag5(3,5-(CF3)2Pz)6(CH3CN)]− (L = 2-(N,N-diethylanilino-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) shows bright and tunable emissions influenced by its supramolecular structure. Columnar stacks are assembled via cooperative interactions that include AgI⋯AgI argentophilic bonding, π⋯π stacking and AgI⋯π interactions.