Faculty of Chemistry , Jagiellonian University , Gronostajowa 2 , 30-387 Kraków , Poland.
Institut für Anorganische Chemie , Christian-Albrechts-Universität , Max-Eyth.-Str. 2 , 24118 Kiel , Germany.
Inorg Chem. 2018 Nov 5;57(21):13415-13422. doi: 10.1021/acs.inorgchem.8b01992. Epub 2018 Oct 19.
The coexistence of dehydration-driven charge transfer, magnetic interactions, and high proton conductivity was found in two bimetallic alternating CN-bridged chains {(HO)[Ni(cyclam)][M(CN)]·5HO} (M = Ru (1), Os (2); cyclam = 1,4,8,11-tetraazacyclotetradecane). Dehydration of these materials causes structural transformation and triggers charge transfer between the metal centers: Ni-NC-M → Ni-NC-M. The CT process, whose extent is tuned by the change of the anionic building block, causes significant increase of magnetic moment, appearance of antiferromagnetic interactions, and noticeable changes in color. The high conductivity values of σ = 1.09 × 10 (1) and 1.12 × 10 S cm (2) at 295 K and 100% relative humidity allow the classification of the materials as superionic conductors. The proton conduction occurs according to the Grotthuss mechanism as a hopping of protons between H-bonded water molecules due to the presence of the HO ions, which compensate negative charge of the coordination chains.
在两个双金属交替的 CN 桥联链中发现了脱水驱动的电荷转移、磁相互作用和高质子传导性{(HO)[Ni(cyclam)][M(CN)]·5H2O}（M = Ru（1），Os（2）；cyclam = 1,4,8,11-四氮杂环十四烷）。这些材料的脱水导致结构转变，并在金属中心之间引发电荷转移：Ni-NC-M → Ni-NC-M。CT 过程的程度可以通过改变阴离子构建块来调节，导致磁矩显著增加、出现反铁磁相互作用以及颜色发生明显变化。在 295 K 和 100%相对湿度下，σ = 1.09×10(1)和 1.12×10 S cm(2)的高电导率值使这些材料被归类为超离子导体。质子传导根据 Grotthuss 机制发生，由于存在 HO 离子，质子在氢键水分子之间跳跃，从而补偿配位链的负电荷。
