An Organic–Inorganic Hybrid Exhibiting Electrical Conduction and Single‐Ion Magnetism. (21st January 2020)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Angewandte Chemie. Volume 132:Number 6(2020)
• Page Start: 2420
• Page End: 2427
• Publication Date: 2020-01-21
• Subjects: 3D-Netzwerke -- Ladungstransfer -- Kristalline Feststoffe -- d-pi-Wechselwirkungen -- Elektrische Leitfähigkeit; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201910523
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The first three‐dimensional (3D) conductive single‐ion magnet (SIM), (TTF)2 [Co(pdms)2 ] (TTF=tetrathiafulvalene and H2 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 [HNEt3 ]2 [M(pdms)2 ] (M=Co, Zn) allow for multiple charge transfers (CTs) between the SIM donor [M(pdms)2 ] n − 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)2 ] n − 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)2 [Co(pdms)2 ] (2‐Co ) is an excellent building block for preparing new conductive SIMs. Abstract : Magnetische Anziehung : Die Elektrokristallisation von Tetrathiafulvalen (TTF) und dem magnetischen Vorläufer [Co(pdms)2 ] (H2 pdms=1, 2‐Bis(methansulfonamido)benzol) liefert einen leitfähigen Einzelionenmagneten. Multiple Ladungstransferwechselwirkungen zwischen den Komponenten erzeugen partielle Oxidationsstufen für TTF, das Co‐Ion und den pdms‐Liganden, die eine elektrische Leitfähigkeit bei niedrigen Temperaturen ermöglichen.