Stacking Principles on π- and Lamellar Stacking for Organic Semiconductors Evaluated by Energy Decomposition Analysis

Two stacking manners, that is, π- and lamellar stacking, are generally found for organic semiconductors, in which the π-stacking occurs between conjugated groups and the lamellar stacking refers to the separation of the conjugated and aliphatic moieties. The stacking principles are yet not well-defined. In this work, extended transition state–natural orbitals for chemical valence (ETS–NOCV), an energy decomposition analysis, is utilized to examine the π- and lamellar stacking for a series of naphthalenetetracarboxylic diimide (R-NDI) crystals. The crucial role of dispersion is validated. The perception that π-stacking is merely determined by the conjugated moiety is challenged. The stacking principles are associated with the closest packing model. Nanoscopic phase separation of conjugated and aliphatic moieties and the formation of lamellar and herringbone motifs in the R-NDIs can thus be clarified. Moreover, the interactions between NDI and the alkyl chain are investigated, revealing that the interactions can be significant, being contradictory to the conventional point of view. Along with R-NDIs, additional organic crystals consisting of various conjugated functionalities and substituents are also investigated by ETS–NOCV. The sampling scope is up to 108 conjugated molecules. The dominant role of dispersion force irrespective of the variation in the conjugated moieties and substituents is further confirmed. It is envisaged that the established principles are applicable to other organic semiconductors. The perspective toward the π- and lamellar stacking might be modified, paving the way for ultimate morphological control.