Non-covalent interactions between cations in the crystal structure of [Pt{4′-(p-tolyl)trpy}Cl]SbF6, where trpy is 2,2′:6′,2″-terpyridine, underpin the salt's complex solid-state luminescence spectrum

► Cations of [Pt{4′-(p-tolyl)trpy}Cl]SbF6 (trpy = 2,2′:6′,2″-terpyridine) stack in columns. ► Each cation is near-planar with the tolyl ring canted 9.3° out of the trpy ligand plane. ► The cations form inversion pairs (dimers) stabilized by short Pt···Pt interactions (3.434(1) Å). ► Unique π(trpy)-π(tolyl) interactions contribute to a complex solid emission spectrum at 77 K. ► Band maxima were assigned to 3MLCT (554 nm), 3MMLCT (604 nm), and excimeric 3π-π∗ (645 nm) states.