Tuning the Crystal Structure of Amphiphilic 3,4,5-Tris(alkyloxy)benzenesulfonates with Bulky Tetrabutylammonium...

3,4,5-Tris(alkyloxy)benzenesulfonates constitute a class of wedge-shaped dendrons exhibiting liquid crystalline properties, characterized by a diverse and intricate phase behavior that is predominantly governed by the length of the terminal aliphatic chains and the size and nature of the dendrons' focal group, which collectively influence their self-organization. In systems comprising both two large counterions-wedge-shaped 3,4,5-tris(alkyloxy)benzenesulfonate anions and tetrabutylammonium (N(C₄H₉)₄⁺) cations-a delicate balance between ionic interactions and microphase segregation drives the formation of giant octupoles that self-assemble subsequently into a remarkably ordered lattice. Such phase behavior is consistently observed across a broad range of compounds, with terminal aliphatic chain lengths varying from six to eighteen methylene units. While the structural configuration of the octupoles and the resulting crystalline lattice remains consistent across most compounds, a distinct transition from quantitative to qualitative changes is observed in tetrabutylammonium 3,4,5-tris(hexadecyloxy)benzenesulfonates and 3,4,5-tris(octadecyloxy)benzenesulfonates that exhibit a unique crystalline lattice structure.