Hydrogen
bonds are among the most common interactions used by nature
for the creation of hierarchical structures from smaller building
blocks. Herein, we describe an in-depth study of the hierarchical
assembly of cylindrical block comicelles with a crystallizable poly(ferrocenyldimethylsilane)
(PFS) core via H-bonding interactions to form complex supermicellar
structures. Well-defined block comicelles bearing H-bond donor (HD) segments (M(PFS-b-PMVSOH)), or H-bond acceptor
(HA) segments (M(PFS-b-P2VP)), and non-interacting
(N) segments (M(PFS-b-PtBA)) were created by the
living crystallization-driven self-assembly (CDSA) method [PMVSOH
= hydroxyl-functionalized poly(methylvinylsiloxane), P2VP
= poly(2-vinylpyridine), PtBA = poly(tert-butyl
acrylate), M = micelle segment]. Due to the control provided by the
living CDSA approach, both the block comicelles and the individual
segments were virtually monodisperse in length, which facilitated
their predictable hierarchical assembly into higher-level structures.
Two cases were investigated in detail: first, the interaction of N-HA-N triblock comicelles with the HD homopolymer
PMVSOH, and second, the interaction of N-HD-N triblock
comicelles with very short HA cylinders (seeds). By manipulation
of several factors, namely coronal steric effects (via the PtBA corona
chain) and attractive interaction strength (via the H-bonding interaction
between P2VP and PMVSOH), the aggregation of the triblock comicelles
could be controlled, and well-defined multi-micrometer-size structures
such as “shish-kebab”-shaped supermicelles were prepared.
The ability of the seeds adsorbed on the block comicelles to function
as initiators for living CDSA to generate fence-like “shish-kebab”
superstructures was also explored.