Molecular‐Curvature‐Induced Spontaneous Formation of Curved and Concentric Lamellae through Nucleation

Abstract

Spontaneous formation of concentric lamellae was observed in self-assembling giant surfactants consisting of a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) head and flexible polymer tail(s). Owing to the asymmetrical sizes of the head and tail blocks and the rectangular molecular interface, the giant surfactants assumed a truncated-wedge-like molecular shape, which induced morphological curvature during self-assembly, thus resulting in the formation of curved and concentric lamellae. These curved/concentric lamellae were observed in FPOSS-based giant surfactants with different architectures and compositions. The spontaneous curvature formation not only promotes our fundamental understanding of assembly principles, but also provides a promising and efficient approach to the fabrication of a wide range of high-performance devices.

Macromolecular Isomerism in Giant Molecules

“…[33] Moreover,t he overall truncated-wedge-like shape of these giant surfactants leads to the formation of unconventional curved/concentric lamellar morphologies. [34] Therefore, it is clear that topology variation could not only causec hanges of feature sizes, but also may vary the phases entirely.…”

“…(a) Phasediagrams of DPOSS-nPS m (n is the number of tails and m is the degree of polymerization of the PS tail) giantsurfactants and (b) cartoons of FPOSS-PS-b-PEO and PS-(FPOSS)-PEO topo-isomer and the self-assembly mechanism to form the curved/concentric lamellar morphologies. Adaptedw ith permission from Reference[31],Copyright (2016) National Academy of Sciences,and Reference[34],Copyright (2015) John Wiley& Sons, Inc.…”

Discovery of Structural Complexity through Self‐Assembly of Molecules Containing Rodlike Components

“…Further study of the self‐assembly of FPOSS‐based giant surfactants leads to the discovery of the spontaneous formation of curved LAM (Figure I) and concentric LAM phases (Figure II) . Among self‐assembly of conventional diblock copolymers, the microphase separation of two blocks leads to polymeric domains.…”

Smart Transformation of a Polyhedral Oligomeric Silsesquioxane Shell Controlled by Thiolate Silver(I) Nanocluster Core in Cluster@Clusters Dendrimers

“…[7][8][9][10] Thereadily tunable peripheral groups facilitate the rigid POSS as building blocks for the formation of high-ordered structures driven by intermolecular interactions such as hydrogen bonding [11] and metal coordination [12] to assemble coordination polymers.Recently, by coordination of thiol À POSS ligand with Cu I complex, anovel structure-defined 3D complex containing tetranuclear copper(I) cluster as secondary building unit has been demonstrated, [12b] indicating that the thiolÀPOSS is aversatile candidate in the design of metal cluster compounds.Inspired by this,w ec onsider that the thiol-POSS can be used as protecting shell ligands to induce the formation of new silver(I)-POSS cluster compounds, [13,14] which have never been reported. [7][8][9][10] Thereadily tunable peripheral groups facilitate the rigid POSS as building blocks for the formation of high-ordered structures driven by intermolecular interactions such as hydrogen bonding [11] and metal coordination [12] to assemble coordination polymers.Recently, by coordination of thiol À POSS ligand with Cu I complex, anovel structure-defined 3D complex containing tetranuclear copper(I) cluster as secondary building unit has been demonstrated, [12b] indicating that the thiolÀPOSS is aversatile candidate in the design of metal cluster compounds.Inspired by this,w ec onsider that the thiol-POSS can be used as protecting shell ligands to induce the formation of new silver(I)-POSS cluster compounds, [13,14] which have never been reported.…”

“…Polyhedral oligomeric silsesquioxane (POSS) denotes ac lass of small silica nanclusters/nanoparticles with ar igid cage-like RSiO 1.5 conformation featuring attractive thermal and mechanical properties. [7][8][9][10] Thereadily tunable peripheral groups facilitate the rigid POSS as building blocks for the formation of high-ordered structures driven by intermolecular interactions such as hydrogen bonding [11] and metal coordination [12] to assemble coordination polymers.Recently, by coordination of thiol À POSS ligand with Cu I complex, anovel structure-defined 3D complex containing tetranuclear copper(I) cluster as secondary building unit has been demonstrated, [12b] indicating that the thiolÀPOSS is aversatile candidate in the design of metal cluster compounds.Inspired by this,w ec onsider that the thiol-POSS can be used as protecting shell ligands to induce the formation of new silver(I)-POSS cluster compounds, [13,14] which have never been reported. On the one hand, the designed Ag 12 @POSS 6 multiple heteoroclusters may combine the physicochemical properties ascribed to silver(I) cluster and POSS components, which forms anew family of cluster@clusters multifunctional compounds.O nt he other hand, if the silver(I) cluster is protected by cage POSS ligands,the steric hindrance between neighboring shell POSS ligands allows more small auxiliary ligands,such as solvent ligands and counter anion of silver(I) salt, to coordinate to the central silver(I) core.Asaresult, the auxiliary ligands induced silver(I) core transformation may be observed.…”