Comparative studies of the noncovalent interactions in the single‐crystal packing of pyrene, pyrene‐4,5‐dione, and pyrene‐4,5,9,10‐tetraone

Abstract Pyrene‐4,5‐dione and pyrene‐4,5,9,10‐tetraone are K‐region oxidized derivatives of pyrene, which show interesting structural and electronic properties as well as useful application in organic electronic and optoelectronic devices. The single‐crystal structures of pyrene and pyrene‐4,5‐dione have been published, but the crystallographic data of pyrene‐4,5,9,10‐tetraone has not. In this work, the single‐crystal structure of pyrene‐4,5,9,10‐tetraone has been clearly elucidated for the first time, and the detailed crystallographic properties were analyzed and discussed in comparison with those of pyrene and pyrene‐4,5‐dione. Various noncovalent interactions taking place within the supramolecular assemblies that exist in the crystal packing of these compounds were studied by Hirshfeld surface analysis and density functional theory (DFT) calculations. Our joint experimental and computational analyses provide fundamental understanding of the electron density properties, interaction energies, and frontier molecular orbital (FMO) properties for these pyrene systems and establish correlations of these properties with diverse supramolecular assembling motifs.