Shen Yongbing, Cosquer Goulven, Ito Hiroshi, Izuogu David C, Thom Alex J W, Ina Toshiaki, Uruga Tomoya, Yoshida Takefumi, Takaishi Shinya, Breedlove Brian K, Li Zhao-Yang, Yamashita Masahiro
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578, Sendai, Japan.
Present address: Research Group of Solid Material Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima, 739-8526, Japan.
Angew Chem Int Ed Engl. 2020 Feb 3;59(6):2399-2406. doi: 10.1002/anie.201910523. Epub 2020 Jan 21.
The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF) [Co(pdms) ] (TTF=tetrathiafulvalene and H pdms=1,2-bis(methanesulfonamido)benzene), was electrochemically synthesised and investigated structurally, physically, and theoretically. The similar oxidation potentials of neutral TTF and the molecular precursor [HNEt ] [M(pdms) ] (M=Co, Zn) allow for multiple charge transfers (CTs) between the SIM donor [M(pdms) ] and the TTF acceptor, as well as an intradonor CT from the pdms ligand to Co ion upon electrocrystallisation. Usually TTF functions as a donor, whereas in our system TTF is both a donor and an accepter because of the similar oxidation potentials. Furthermore, the [M(pdms) ] donor and TTF acceptor are not segregated but strongly interact with each other, contrary to reported layered donor-acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with CT, allow for relatively high electrical conductivity even down to very low temperatures. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops was observed. (TTF) [Co(pdms) ] (2-Co) is an excellent building block for preparing new conductive SIMs.
首个三维（3D）导电单离子磁体（SIM），(TTF)[Co(pdms) ]（TTF = 四硫富瓦烯，H pdms = 1,2 - 双（甲磺酰胺基）苯），通过电化学合成，并进行了结构、物理和理论研究。中性TTF与分子前驱体[HNEt ][M(pdms) ]（M = Co、Zn）相似的氧化电位，使得在SIM供体[M(pdms) ]和TTF受体之间发生多次电荷转移（CTs），以及在电结晶时从pdms配体到Co离子的供体内CT。通常TTF作为供体，而在我们的体系中，由于相似的氧化电位，TTF既是供体又是受体。此外，与报道的层状供体 - 受体电导体相反，[M(pdms) ]供体和TTF受体并未分离，而是彼此强烈相互作用。强分子间和分子内相互作用与CT相结合，即使在非常低的温度下也能实现相对较高的电导率。此外，还观察到具有慢磁弛豫和磁滞回线开口的SIM行为。(TTF)[Co(pdms) ]（2 - Co）是制备新型导电SIMs的优良结构单元。
