The glass transition temperatures (Tg) of all ag[TBuA][M(dca)3] and ag [TPnA][M(dca)3] (M = Mn, Fe, Co) melt-quenched glasses were obtained in DSC experiments each case (Fig. ). Complete cycles of heating-cooling-heating runs are shown in the supporting information (Fig. broadly consistent with both their low Tm values (185 °C -106 °C), and the empirical "Tg/Tm ~ 2/3" law (Table ). Their location below room temperature is similar to the behaviour of dca based ILs, which generally exhibit glass transitions below room temperature (e.g. -67 °C for [N8444][dca]).