Uniform, High-Aspect-Ratio, and Patchy 2D Platelets by Living Crystallization-Driven Self-Assembly of Crystallizable Poly(ferrocenyldimethylsilane)-Based Homopolymers with Hydrophilic Charged Termini

Two-dimensional (2D) seeded growth of poly(ferrocenyldimethylsilane) (PFS) homopolymers that possess hydrophilic charged termini in solution has been investigated using the living crystallization-driven self-assembly method. Charge-terminated homopolymers, PFSn[NMe3]I were synthesized through a combination of living anionic polymerization and post-polymerization thiol-ene “click” chemistry. Uniform and patchy high-aspect-ratio 2D structures were obtained by seeded growth in solution. We show that the aspect-ratio of the resultant 2D platelets could be controlled over a wide range (ca. 2 – 20) by changing either the solvent polar-ity of the medium in which seeded growth was conducted, the substituents on the charged terminal group, or characteristics of the seed micelle. The counteranion associated with the charge-terminated PFS[NMe3]+ ho-mopolymers was found to have a substantial effect on the resulting morphology and colloidal stability of the resulting 2D platelets and this may be a consequence of relatively high charge-density of the terminal qua-ternary ammonium cation.