The rational design and construction of metallomacrocycles, switchable metallosupramolecular cages, and hierarchically self-assembled nanomaterials will be presented.<sup>[1]</sup> Precise control over both self-assembly processes and conformational interconversions is a big challenge due to the complexity of building blocks and difficulty in controlling the inherently weak, non-covalent interactions. To achieve this goal, we explored a new way to better control structural selectivity by combining directed geometry and modeling, rigid designer monomers, and variable coordination bonds along with dynamic and thermodynamic parameters. Adoption of tailored terpyridine-based building blocks and different metal ions (Ru, Os, Fe, Zn, and/or Cd) gave metallosupramolecular cages with tunable conformations responding to specific stimuli, such as concentration, temperature, and counter ions.<sup>[2,3]</sup> Moreover, further self-assembly beyond the supramacro- molecule will be discussed. Utilizing shape-tuned monomers possessing expanded hydrophobic effects, a series of made-to-order, shape-persistent supramolecules with a rigid triangular framework assemble into highly complementary nanobowls, which open avenues to develop smart designer materials.

From metallomacrocycles to tunable metallosupramolecular cages and materials

254th National Meeting (2017)

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