Co‐Crystal Formation of Partially Fluorinated 1,3,5‐Tris(phenylethynyl)benzenes

Several rigid 1,3,5‐tris(phenylethynyl)benzenes with different fluorination patterns were synthesized through selective Sonogashira‐Hagihara coupling reactions to analyze the packing behavior in solid‐state structures. The aggregation is dominated by various intermolecular interactions between aryl substituents, triple bonds, C−H bonds and H⋅⋅⋅F contacts. Co‐crystallization experiments for the analysis of preferred aryl‐aryl‐interactions led to 1 : 1 complexes. Intermolecular phenyl‐perfluorophenyl interactions with short centroid‐centroid distances are dominating these co‐crystal structures. They lead to melting point increases of up to 49 °C for the co‐crystals compared to the pure substances. π‐Stacking in co‐crystals of fluorinated and non‐fluorinated aryl units in 1,3,5‐tris(phenylethynyl)benzenes have different preferences and give stacks of different stability.