An Organic–Inorganic Hybrid Exhibiting Electrical Conduction and Single‐Ion Magnetism

The first three–dimensional (3D) conductive single-ion magnet (SIM), (TTF)2[Co(pdms)2] (TTF = tetrathiafulvalene and H2pdms = 1,2-bis(methanesulfonamido)benzene), was electrochemically synthesized and investigated structurally, physically and theoretically. The quite close oxidation potential between neutral TTF and the coordination precursor, (HNEt3)2[M(pdms)2] (M = Co, Zn) causes multiple charge transfers (CTs) between SIM donor [M(pdms)2]n– and the TTF●+ acceptor as well as an intra-donor CT from the pdms ligand to Co ion upon electrocrystallization. Usually TTF works as a donor, whereas in our system, TTF works as both a donor and an accepter due to the close 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 the CT, cause relatively high electrical conductivity to very low temperature. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops were observed. (TTF)2[Co(pdms)2] (2-Co) is an excellent building block for preparing new conductive SIM.