Selective assemblies of giant tetrahedra via precisely controlled positional interactions

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Science  24 Apr 2015:
Vol. 348, Issue 6233, pp. 424-428
DOI: 10.1126/science.aaa2421

Creating unusual nanostructures

Self-assembly often occurs when dissimilar molecular fragments are forced together by covalent bonding. Surfactants or block copolymers are two common examples. Huang et al. grafted four different nanoparticles, based on polyhedral oligomeric silsesquioxanes with slightly different compositions, onto a single tetrahedal core (see the Perspective by Yang). Depending on the type of nanoparticle, they assembled into a range of defined, ordered supramolecular lattices similar to a range of metal alloys. These include phases that have higher coordination numbers than usually found in the packing of spherical objects.

Science, this issue p. 424; see also p. 396


Self-assembly of rigid building blocks with explicit shape and symmetry is substantially influenced by the geometric factors and remains largely unexplored. We report the selective assembly behaviors of a class of precisely defined, nanosized giant tetrahedra constructed by placing different polyhedral oligomeric silsesquioxane (POSS) molecular nanoparticles at the vertices of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces precise positional interactions and results in diverse selectively assembled, highly ordered supramolecular lattices including a Frank-Kasper A15 phase, which resembles the essential structural features of certain metal alloys but at a larger length scale. These results demonstrate the power of persistent molecular geometry with balanced enthalpy and entropy in creating thermodynamically stable supramolecular lattices with properties distinct from those of other self-assembling soft materials.

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