Rational Design of Lamellar π–π Stacked Organic Crystalline Materials with Short Interplanar Distance

Organic crystalline materials having a lamellar π–π stacked structural motif with short interplanar distance are significant for many applications. By asymmetrically introducing perfluoroalkyl substituents onto and polarizable sulfur atoms into N-containing heteroaromatics, we successfully synthesized a novel type of aromatic material that preferentially forms lamellar π–π stacked crystalline materials with a interplanar π–π distance of 3.247 Å, more than 0.1 Å shorter than that of highly oriented pyrolytic graphite (HOPG) where interplanar distance ranges from 3.35 to 3.39 Å.