Organic Hybrid Antimoniotungstate Layered Ionic Crystal: Synthesis, Structure, and Interlayer-Confined Proton Conduction

A synchronous crystal- and microstructure-dependent strategy was implemented to synthesize the organic hybrid antimoniotungstate layered ionic crystal Na_5.5H_6.5[(SbW₉O₃₃)₂{WO₂(OH)}₂{WO₂}RuC₇H₃NO₄]·36H₂O, and the layered structure was constructed through the Na⁺ bridged sheet and the hydrogen-bonded layers. It displayed an effective proton conductivity of 2.97 × 10^-2 S cm^-1 at 348 K and 75% RH, owing to the complete interlayer confined hydrogen-bond network formed by the hydrogens of interlayer crystal waters, organic ligands ({RuC₇H₃NO₄}²⁺, {C₇H₃NO₄} is formed by the hydrolysis of pyridine 2,5-dicarboxylic acid (C₇H₅NO₄)), and acidic protons (H⁺), along with the interlayer domain as a transport channel. Furthermore, the hydrogen-bond network originating from interlayer organic ligands and acidic protons was more stable at a higher temperature of 423 K, preserving a high conductivity of 1.99 × 10^-2 S cm^-1.