Block copolymers (BCPs) are ideal building blocks for a variety of nanoscale objects due to their ability to undergo spontaneous phase separation in selective solvents.1 Our group has previously shown that BCPs with a metal-containing poly(ferrocenyldimethylsilane) (PFS) core-forming block can be used to prepare well-defined nanostructures via a crystallization-driven self-assembly (CDSA) process in solution that resembles a living covalent polymerisation2. The self-assembly of crystalline-coil BCPs in thin films and the bulk phase has been exploited for the fabrication of nanoscale domains with a diverse range of patterns.3 However, examples of cylindrical micelles with coronas that undergo spontaneous phase segregation during solution CDSA are rare. We report studies of the CDSA of a series of crystalline-brush BCPs with n-alkyl branches. When co-crystallized with a linear BCP, the resulting micelles displayed chemically nanosegregated coronas where the size and frequency of compartmentalisation could be controlled by the ratio of linear to brush BCP. Furthermore, the co-crystallisation occurred in a gradient, with an initial bias for the growth of the linear BCP over that of the more sterically demanding brush BCP. This result represents the first example of living gradient CDSA, an analogous process to a covalent gradient copolymerisation.F. H. Schacher, P. Rupar, & I. Manners. Angew. Chem. Int. Ed., 2012, 51(32), 7898�921.T. G�dt, N. S. Ieong, G. Cambridge, M. A. Winnik, and I. Manners, Nat. Mater., 2009, 8, 144�150.V. P. Chuang, J. Gwyther, R. a Mickiewicz, I. Manners, and C. a Ross, Nano Lett., 2009, 9, 4364�4369.J. B. Gilroy, T. G�dt, G. R. Whittell, L. Chabanne, J. M. Mitchels, R. M. Richardson, M. A. Winnik, and I. Manners, Nat. Chem., 2010, 2, 566�570.

Gradient crystallization-driven self-assembly: Co-assembly of crystalline-coil polyferrocenylsilane block copolymers

248th National Meeting (2014)

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