Size and Shape Manipulation of Channel Structures Assembled Via Saddle stacking of Tetrapodal Adamantanes Containing Aryl Butadiynyl Moieties

Abstract

Three tetrapodal adamantane derivatives containing aryl butadiynyl moieties were synthesized under conditions similar to those of the Hay coupling reaction, and their crystal structures were analyzed. The substituted tetrapodal adamantanes were found to pile atop each other via saddle stacking to form 1D columnar structures, and the assembly of these 1D structures gave rise to channels in the crystal. Column assembly was achieved through CH/π and π-π interactions between the terminal aromatic rings of the adamantanes belonging to adjacent columns. The channels thus formed had different shapes and sizes depending on the terminal aryl substituents, and were occupied by a suitable number of solvent molecules. Compared to the adamantanes with phenyl butadiynyl moieties as the terminal substituents, those with naphthyl butadiynyl moieties formed wider or thicker channels owing to their greater expanse perpendicular to the direction of saddlestacking.