The Peter Day Series of Magnetic (Super)Conductors

Here, we review the different series of (super)conducting and magnetic radical salts prepared with organic donors of the tetrathiafulvalene (TTF) family and oxalato-based metal complexes (ox = oxalate = C2O42−). Although most of these radical salts have been prepared with the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF = ET), we also include all the salts prepared with other TTF-type donors such as tetrathiafulvalene (TTF), tetramethyl-tetrathiafulvalene (TM-TTF), bis(ethylenediseleno)tetrathiafulvalene (BEST), bis(ethylenedithio)tetraselenafulvalene (BETS) and 4,5bis((2S)-2-hydroxypropylthio)-4’,5’-(ethylenedithio)tetrathiafulvalene (DMPET). Most of the oxalate-based complexes are monomers of the type [MIII(C2O4)3]3−, [Ge(C2O4)3]2− or [Cu(C2O4)2]2−, but we also include the reported salts with [Fe2(C2O4)5]4− dimers, [MII(H2O)2[MIII(C2O4)3]2]4− trimers and homo- or heterometallic extended 2D layers such as [MIIMIII(C2O4)3]− and [MII2(C2O4)3]2−. We will present the different structural families and their magnetic properties (such as diamagnetism, paramagnetism, antiferromagnetism, ferromagnetism and even long-range magnetic ordering) that coexist with interesting electrical properties (such as semiconductivity, metallic conductivity and even superconductivity). We will focus on the electrical and magnetic properties of the so-called Day series formulated as β”-(BEDT-TTF)4[A+MIII(C2O4)3]·G, which represents the largest family of paramagnetic metals and superconductors reported to date, with more than fifty reported examples.