Organized Nanostructured Complexes of Inorganic Clusters and Surfactants That Exhibit Thermal Solid‐State Transformations

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Abstract
Facile organization of the inorganic crown‐shaped [Ni3P3S12]3− ion (1) into room‐temperature liquid‐crystalline materials by complexation with double‐tail ammonium surfactants is achieved by the ionic self‐assembly (ISA) route. Small‐angle Xray diffraction, UV/Vis spectroscopy, and 31P NMR analyses reveal that these complexes show an interesting solid‐state structure transition. Upon heating, the inorganic crown species polymerizes to the inorganic polyelectrolyte $\rm{^{1}_{\infty }}$[NiPS4]−. This structural transition is reversible, and involves a solvent/dissolution cycle. The facile preparation and facile optional induction of phase and structural changes make these complexes candidates for a number of applications in which cooperative, metastable switching with sufficient contrast of optical and solid‐state properties is required.

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