Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents

The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 mu m after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.