ja6b06712_si_001.pdf (1.79 MB)
Download fileBlock Co-PolyMOCs by Stepwise Self-Assembly
journal contribution
posted on 27.07.2016, 00:00 authored by Yufeng Wang, Mingjiang Zhong, Jiwon
V. Park, Aleksandr V. Zhukhovitskiy, Weichao Shi, Jeremiah A. JohnsonWe
report a stepwise assembly strategy for the integration of metal–organic
cages (MOCs) into block copolymers (BCPs). This approach creates “block
co-polyMOC” (BCPMOC) materials whose microscopic structures
and mechanical properties are readily tunable by adjusting the size
and geometry of the MOCs and the composition of the BCPs. In the first
assembly step, BCPs functionalized with a pyridyl ligand on the chain
end form star-shaped polymers triggered by metal-coordination-induced
MOC assembly. The type of MOC junction employed precisely determines
the number of arms for the star polymer. In the second step, microphase
separation of the BCP is induced, physically cross-linking the star
polymers and producing the desired BCPMOC networks in the bulk or
gel state. We demonstrate that large spherical M12L24 MOCs, small paddlewheel M2L4 MOCs,
or a mixture of both can be incorporated into BCPMOCs to provide materials
with tailored branch functionality, phase separation, microdomain
spacing, and mechanical properties. Given the synthetic and functional
diversity of MOCs and BCPs, our method should enable access to BCPMOCs
for a wide range of applications.