Unraveling the Self-Assembly of Heterocluster Janus Dumbbells into Hybrid Cubosomes with Internal Double-Diamond Structure

Abstract

Cubosomes are bicontinuous cubic-phase particles generated by amphiphile self-assembly with bicontinuous cubic phases, which creates an intricate network of interconnected nanochannels that endow these materials with special functions for advanced applications. On the other hand, clusters are an attractive class of molecules that exhibit intriguing functions and properties that differ from those of atoms and nanoparticles. Inspired by lipid self-assembly and attracted to the new functionalities of clusters, we prepared special heterocluster Janus dumbbells (HCJDs) composed of dissimilar nanoclusters: namely, a polyoxometalate and a polyhedral oligomeric silsesquioxane. HCJDs resemble conventional amphiphiles and, as such, they self-assemble in solution into faceted hybrid cubosomes via the transformation of vesicles into spongelike aggregates. Multiple mechanisms that lead to equilibrium, including molecular self-assembly, vesicle accumulation, membrane fusion, inner-structure reorganization, and cubic crystal growth, contributed to the overall process. On the basis of these results, we proposed a strategy for self-assemblyfrom basic molecular design that goes beyond traditional amphiphiles to the construction of micro-or nanomaterials with hierarchical structures and advanced functions.

Polyoxometalate Clusters: Sub-nanometer Building Blocks for Construction of Advanced Materials

“…(D) The nanotube structures through helical self-assembly in acetone/n-hexane system. Reprinted with permission from Ren et al 111 113 Copyright 2018, American Chemical Society.…”

“…The acetone/n-decane system is subsequently processed and the Janus clusters are prepared with the aforementioned POM and POSS clusters before being linked by various organic linkers. 113 The Janus dumbbells can self-assemble into faceted hybrid cubosomes in acetone/n-decane (3:2 volume ratio) driven by solvent evaporation (i.e., to decrease acetone content via evaporation). The self-assembly process and morphology evolution of aggregates are shown in Figure 7H, and the faceted particle with an ordered nanostructure can be achieved after aging for 10 h (Figure 7I).…”

Direct observation of charge transfer between molecular heterojunctions based on inorganic semiconductor clusters

“…Over the past decade, crystalline molecular heterojunctions, [13][14][15][16][17] especially those with strongly bonded interfaces, have drawn much attention because of their ideal contact areas, bonding sites between adjacent molecules (or phases), and controllable compositions in ultra-small subunits. [18][19][20][21] This well-dened heterostructured conguration offers obvious advantages for photovoltaic and catalytic applications, as the sufficient hybridization of atomic orbitals permits efficient carrier delocalization and allows programmable band structures to meet the potential of catalytic reactions.…”

Single molecule–mediated assembly of polyoxometalate single-cluster rings and their three-dimensional superstructures

“…Kovalenko and co-workers (27) have achieved a family of superlattices assembled by POM clusters and inorganic nanocrystals. Recently, Wang and co-workers (28) reported the double-diamond cubosome superstructures built by heterocluster Janus dumbbells. However, the superstructure assemblies constructed by single POM clusters have not been reported yet.…”