Organized nanostructured complexes of inorganic clusters and surfactants that exhibit thermal solid-state transformations

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 X-ray diffraction, UV/Vis spectroscopy, and P-31 NMR analyses reveal that these complexes show an interesting solid-state structure transition. Upon heating, the inorganic crown species polymerizes to the inorganic polyelectrolyte (1)(infinity)[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.