Living Self-Assembly of Metastable and Stable Two-Dimensional Platelets from a Single Small Molecule

This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated level of a solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures. The living seeded self-assembly of metastable and stable 2D structures with uniform shapes and precise sizes can be achieved using an appropriate supersaturated level of a solution of 1 as the growth medium that can temporarily hold the almost-proceeding spontaneous nucleation. This new methodology allows the living self-assembly of small molecules to proceed in two independent steps, i. e., the design of molecules for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes, thus rendering a convenient and adaptable methodology for novel architectures.+image