The structure and phase behavior of colloidal solutions of monodisperse rod-shaped micelles, of different lengths (ca. 300–2100 nm) and formed from poly(ferrocenylsilane)-block-polyisoprene (PFS-b-PI) diblock copolymers, have been investigated using synchrotron small-angle X-ray scattering. The dimensions of the crystalline PFS core, solvated PI corona, and the overall radial polydispersity were measured, and relationships between the characteristics of the constituent copolymers and the internal structure of the self-assembled micelles have been established. In addition, the effects of micelle length, length distribution, concentration, composition, and block length on the liquid crystalline phase behavior of the micelles have been determined. It was found that micelle dispersions exist in three distinct phases: isotropic, nematic, and hexagonally packed, depending predominantly on their concentration and aspect ratio. The results have also highlighted the importance of the coronal composition and structure in determining the high-concentration behavior of micelle dispersions.

Block copolymers (BCPs) with a short crystallizable poly(ferrocenyldimethylsilane) (PFS) core-forming block self-assemble in selective solvents to afford cylindrical micelles, the ends of which are active to further growth via a process termed living crystallization-driven self-assembly (CDSA). We now report studies of the CDSA of a series of crystalline-brush BCPs with C6 (BCP6), C12 (BCP12), and C18 (BCP18) n-alkyl branches that were prepared by the thiol–ene functionalization of PFS-b-PMVS (PMVS = poly(methylvinylsiloxane)). Although the increased n-alkyl brush length of BCP12 and BCP18 hindered micelle growth, the increased intercoronal chain repulsion could be alleviated by their coassembly with linear PFS-b-PMVS. When the coassembly was initiated by short cylindrical seed micelles, monodisperse block comicelles of controllable length with “patchy” coronal nanodomains were accessible. TEM and AFM analysis of micelles prepared from BCP18 and PFS-b-PMVS were found to provide complementary characterization in that the OsO4-stained PMVS coronal domains were observed by TEM, whereas the brush block domains of BCP18 (which displayed greater height) were detected by tapping mode AFM. The results showed that the coassembly afforded a gradient structure, with an initial bias for the growth of the linear BCP over that of the more sterically demanding brush BCP, which was gradually reversed as the linear material was consumed. This represents the first example of living gradient CDSA, a process reminiscent of a living covalent gradient copolymerization of two different monomers. Although other possible explanations exist, simulations based on a statistical model indicated that the coronal nanodomains detected likely result from a segmented, gradient comicelle architecture that arises as a consequence of: (i) different rates of addition of BCP unimer to the micelle termini, and (ii) a cumulative effect resulting from steric hindrance associated with the brush block.