Given that the coordination chemistry of H4TBC [4] with Mn is very well established, and shown to be a hugely fruitful source of numerous polymetallic clusters, the isolation of only three Mn-based complexes of H8TBC [8] is surprising, in turn suggesting that a systematic investigation of this chemistry has not been performed. Drawing conclusions regarding structural trends is rather difficult, though two of the three metallic skeletons are based on squares. It is interesting to see that all three common Mn oxidations states (Mn II , Mn III and Mn IV ) exist in the three complexes isolated, and all the calix [8]arenes are only partially deprotonated, H4TBC [8] or H5TBC [8]. We also note that in two of the three complexes isolated, molecules not added to the reaction mixtures become incorporated into the structures -CO3 2-from the fixation of CO2, formate from the oxidation of MeOH and dimethylcarbamate from the breakdown of dmf. This perhaps suggests that the deliberate introduction of these (or similar) molecules would be worth exploring. Indeed, the presence of the CO3 2-ion is a common theme in the Ln III -based chemistry discussed below (and in Ln coordination chemistry more generally), but it is very rarely/intentionally employed as a bridging ligand.