Ionic Complexes of Metal Oxide Clusters for Versatile Self-Assemblies.

The combination of rational design of building components and suitable utilization of driving force affords spontaneous molecular assemblies with well-defined nanostructure and morphology over multiple length scales. The serious challenges in constructing assemblies with structural advantages for the realization of functions programmed into the building components usually lie ahead since the process that occurs does not always follow the expected roadmap in the absence of external intervention. Thus, prefabricated intermediates that help in governing the target self-assemblies are developed into a type of unique building blocks. Metal oxide cluster polyanions are considered as a type of molecular nanoclusters with size scale and structural morphology similar to those of many known inorganic particles and clusters but possess distinctive characteristics. Following the understanding of these clusters in self-assembly and the rationalization of their most efficient design strategy and approach, the obtained fundamental principles can also be applied in common nanoparticle- and cluster-based systems. On the other hand, the deliberate synergy offered by organic countercations that support the self-assembly of these clusters greatly expands the opportunity for the functionalization of complex building units via control of multiple interactions. The ionic combination of the inorganic clusters with hydrophilicity and the cationic organic component with hydrophobicity leads to discrete properties of the complexes. Significantly, the core-shell structure with rigid-flexible features and amphiphilicity will pave the way for hierarchical self-assemblies of the obtained complexes, while the intrinsic characteristics of the metal oxide clusters can be modulated through external physicochemical stimuli. Within this context, over the past decade we have extensively explored the ionic combination of inorganic polyanionic clusters with cationic organic amphiphiles and devoted our efforts to establishing the general rules and structure-property relationships of the formed complexes for constructing self-assemblies at the interface, in solution, and in solid matrixes. Specific interest has been focused on the functional synergy deriving from the incompatible components in highly organized self-assemblies. In this Account, we describe the recent progress on the ionic complexation of polyoxometalate clusters with cationic amphiphiles and the construction of diverse self-assembled nanostructures. First, the fundamental structural characteristics and molecular geometries of the prepared complexes are analyzed. The construction principle and diversity of the self-assembly based on the complexes and the smart stimuli response are then discussed, subject to the adjustment of various non-covalent interactions occurring in the assemblies. Subsequently, we enumerate the functional applications of the ionic complexes assembling into organic, inorganic, and even biological matrixes. The inspiration from the construction of ionic complexation and self-assembly in this Account provides vivid profiles for the design of hybrid materials involving nanoclusters and/or nanoparticles with rich potentials in addition to polyoxometalate chemistry.