Journal of the American Chemical Society, Vol.136, No.8, 2974-2977, 2014
Macromolecular Metallurgy of Binary Mesocrystals via Designed Multiblock Terpolymers
Self-assembling block copolymers provide access to the fabrication of various ordered phases. In particular, the ordered spherical phases can be used to engineer soft mesocrystals with domain size at the 5-100 nm scales. Simple block copolymers, such as diblock copolymers, form a limited number of mesocrystals. However multiblock copolymers are capable to form More complex mesocrystals. We demonstrate that designed B(1)AB(2)CB(3) multiblock terpolymers, in which the A- and C-blocks form spherical domains and the packing of these spheres can be controlled by changing the lengths of the middle and terminal B-blocks, self-assemble into various binary mesocrystals with space group symmetries of a large number of binary ionic crystals, including NaCl, CsCl, ZnS, alpha-BN, AlB2, CaF2, TiO2, ReO3, Li3Bi, Nb3Sn(A15), and alpha-Al2O3. This approach can be generalized to other terpolymers as well as to tetrapolymers to obtain ternary mesocrystals. Our study provides a new concept of macromolecular metallurgy for producing crystal phases in a mesoscale and thus makes multiblock copolymers a robust platform for the engineering of functional materials.