Dehydration-Triggered Charge Transfer and High Proton Conductivity in (H3O)[NiIII(cyclam)][MII(CN)6] (M = Ru, Os) Cyanide-Bridged Chains

摘要: The coexistence of dehydration-driven charge transfer, magnetic interactions, and high proton conductivity was found in two bimetallic alternating CN-bridged chains {(H3O)[NiIII(cyclam)][MII(CN)6]·5H2O} n (M = Ru (1), Os (2); cyclam 1,4,8,11-tetraazacyclotetradecane). Dehydration these materials causes structural transformation triggers transfer between the metal centers: NiIII-NC-MII → NiII-NC-MIII. CT process, whose extent is tuned by change anionic building block, significant increase moment, appearance antiferromagnetic noticeable changes color. values σ 1.09 × 10-3 (1) 1.12 S cm-1 (2) at 295 K 100% relative humidity allow classification as superionic conductors. conduction occurs according to Grotthuss mechanism a hopping protons H-bonded water molecules due presence H3O+ ions, which compensate negative coordination chains.