Modularly Constructed Polyhedral Oligomeric Silsesquioxane-Based Giant Molecules for Unconventional Nanostructure Fabrication

Abstract

Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. Here, we report a way to manipulate the supramolecular structures of giant molecules based on discotic triangle cores and isobutyl polyhedral oligomeric silsesquioxanes (BPOSS) nanoparticles (NPs). It is found that depending upon the number of BPOSS at the periphery of the discotic cores, the packing of these nanoscale components (discotic core and POSS) could be manipulated into either cylindrical or Frank−Kasper (F−K) A15 (Pm3̅ n) phases. The formation of these supramolecular nanostructures is mandated by the balance between the stacking of the discotic cores and the steric hindrance effect of the BPOSS NPs. This strategy to manipulate the packing of nanoscale building blocks for different supramolecular nanostructures including the fabrication of cylindrical structures and A15 (Pm3̅ n) phases may be extended to other nanoscale building blocks for future development of materials with complex structures as well as tailored functionalities and properties.

Acetone Factor in the Design of Cu4-, Cu6-, and Cu9-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes

“…Branched silsesquioxane units of [RSiO 1.5 ] n composition are among the most popular blocks for creating numerous hybrid nanomaterials and composites. − Two general approaches in this chemistry are actively developing nowadays(i) the use of fully condensed silsesquioxanes generally based on octameric [RSiO 1,5 ] 8 cubane-like units and (ii) the application of partly condensed derivatives. Among many fascinating and functional structures, available via the first approach, we can mention polyhedral oligomeric silsesquioxanes (POSS) bearing chromophore groups, , materials for sorption of heavy-metal ions/dyes/organic solvents from water, − additives for polymers, components of nanoscale building blocks, , shape amphiphiles, organocatalysts, building blocks for the construction of magnetic materials, and luminescent devices or light-harvesting systems. , …”

Constituent Isomerism-Induced Quasicrystal and Frank–Kasper σ Superlattices Based on Nanosized Shape Amphiphiles

“…10,11 Often, the dodecagonal quasicrystal (DDQC) phase with 12-fold orientational symmetry and only one-dimensional (1D) translational symmetry are closely associated with F-K phases, due to similarities in local tetrahedral packing rules. [12][13][14] Complex F-K phases and the DDQC phase have not only been observed in broad soft matter systems, including diblock copolymers, [15][16][17][18][19][20][21][22][23] dendrimers, 13,[24][25][26][27][28][29][30][31] polymer colloids, 32 small molecular surfactants, [33][34][35] giant molecules, [36][37][38][39][40] and very recently, sugar-polyolefin conjugates, 41,42 but also mesoporous silica, 43,44 binary nanocrystal superlattices, 45,46 and DNA functionalized nanoparticles. 47,48 Several types of F-K phases only have considerably small differences between their overall free energies.…”

Rational Route Toward the Frank–Kasper Z Phase: Effect of Precise Geometrical Tuning on the Supramolecular Assembly of Giant Shape Amphiphiles

“…Using the giant shape amphiphiles developed by our group, we found that much less molecules will be required to form a spherical motif. 23,32,36,40,41 Therefore, the supramolecular assembly of giant shape amphiphiles could be a feasible pathway toward the unusual Z and C15 phases in single-component soft matter. Indeed, in our recent work, we discovered a series of unconventional spherical packing phases in giant shape amphiphiles, including the A15 phase, σ phase, dodecagonal quasicrystalline (DQC) phase, and body-centered cubic (BCC) phase, by functionalization of the perylene core with several polyhedral oligomeric silsesquioxane (POSS) cages.…”