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

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<jats:title>Abstract</jats:title><jats:p>Facile organization of the inorganic crown‐shaped [Ni<jats:sub>3</jats:sub>P<jats:sub>3</jats:sub>S<jats:sub>12</jats:sub>]<jats:sup>3−</jats:sup> ion (<jats:bold>1</jats:bold>) 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 <jats:sup>31</jats:sup>P NMR analyses reveal that these complexes show an interesting solid‐state structure transition. Upon heating, the inorganic crown species polymerizes to the inorganic polyelectrolyte <jats:styled-content>$\rm{^{1}_{\infty }}$</jats:styled-content>[NiPS<jats:sub>4</jats:sub>]<jats:sup>−</jats:sup>. 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.</jats:p>

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