Fluorination‐controlled Aggregation and Intermolecular Interactions in Pt(II) Complexes with Tetradentate Luminophores

In this work we describe the synthesis and DFT‐supported photophysical characterization of a series of Pt(II) complexes bearing tetradentate luminophores with increasing degree of fluorination. Aggregation into crystalline phases leads to substitution‐dependent arrangements that in all cases hinder intermetallic coupling, as intermolecular interactions are dominated by hydrogen bonding and π‐stacking. In amorphous matrices, on the other hand, we observed that an increasing level of fluorination favors the tendency towards Pt−Pt interaction upon aggregation, leading to a red‐shifted phosphorescence, if compared with monomeric species in dilute solutions and crystalline solids.