Co-templating of polyoxoniobates and silicate/germanate trimer-rings in crystals and inorganic gels

Polyoxometalate (POM) supramolecular gels are a growing family of materials, both for understanding fundamental self-assembly and fabricating flexible monolithic materials that retain the function of metal oxides. Here, we exploited the pH-dependent speciation of polyoxoniobates (PONbs), targeting the formation of PONb-containing supramolecular gels that contain other low molecular weight components (silicate, germanate, phosphate, and carbonate). The introduction of gaseous CO₂ into aqueous hexaniobate solutions resulted in the formation of both new crystalline phases and highly transparent gels. The crystalline phases, formulated Cs₂₄[Nb₇O₂₂(NbO(CO₃)₂)₉(Si₃O₉)]·19.6H₂O and Cs₂₁Na₃[Nb₇O₂₂(NbO(CO₃)₂)₉(Ge₃O₉)]·33.6H₂O are templated by a rare planar [X₃O₉]^6- (X = Si, Ge) ring. Crystalline phases were not obtained with phosphate; instead, the gels contain a mixture of phosphate-centred PONbs and network-forming phosphate. POM speciation within the gels, physical properties, and assembly mechanisms were benchmarked by solution and solid-state nuclear magnetic resonance (NMR) spectroscopy, vibrational spectroscopies, small-angle X-ray scattering (SAXS), and thermogravimetry-mass spectroscopy. Optical analysis and dielectric behavior of the gels confirmed that they are highly transparent ionic and electronic conductors. The alkali and hydroxide concentration controls the formation of crystalline materials or supramolecular gels while maintaining the same network building blocks, providing a rare opportunity to describe the molecular-level structure of inorganic amorphous materials.