Kinetically Controlled Polymorphic Superstructures of Pyrene‐Based Asymmetric Liquid Crystal Dendron: Relationship Between Hierarchical Superstructures and Photophysical Properties

: To understand the relationship between kinetically controlled hierarchical superstructures and photophysical properties, pyrene-based asymmetric liquid crystal (LC) dendrons (abbreviated as PD) were newly synthesized by covalently attaching a pyrene moiety (P) at a biphenyl-based LC dendritic group (D). The phase transition behavior of PD has been systematically studied with a combined technique of thermal analysis, microscopy, spectroscopy, and scattering analysis. PD formed two different crystalline structures depending on the cooling rate: a stable crystalline phase (Ks , slow cooling) and a metastable crystalline phase (Kms , quenching). The kinetically controlled molecular packing structures of PD depend on the competition and cooperation of intermolecular physical interactions with nanophase separation. Upon slow cooling, the PD dimer formed by intermoelcular H-bonding constructed a layered hierarchical structure with the help of nanophase separation. Owing to the strong π-π stacking (J-aggregation) with weak H-bondings, the PD dimer in the layer was slightly tilted to give a monoclinic layered structure with a periodic layer d-spacing of 6.6 nm. In contrast, the metastable Kms phase formed by the quenching process showed a significant tilt of the PD dimer in the layer (d-spacing=4.4 nm) due to the weak π-π stacking (H-aggregation) and the strong H-bondings.