Systematic exploration of the coordination chemistry of H4TBC [4] previously allowed us to establish a series of empirical metal ion binding rules that also translate very effectively to H8-bis-TBC [4]. Coordination chemistry is promoted by the common cone conformation adopted by C [4]s, and this may benefit from synthetic modification at the methylene bridge positions in future as this (in principle) does not interfere with the polyphenolic pocket. The larger, odd-numbered homologues of H4TBC [4] hold enormous potential for application in the synthesis of coordination clusters. However, greatly improved synthetic protocols are required for HnTBC [n] where n is 7 or 9 as these would need to be scaled up for exploratory cluster synthesis with a wide range of 3d and 4f ions. In this review we have shown that, to date, a large number of clusters formed using H8TBC [8] as a ligand have been synthesised. Interestingly, only a relatively small number have varying degrees of deprotonation possible in H8TBC [8], coupled with the ability to form homo/heterometallic assemblies, suggests that a systematic study of the associated coordination chemistry of this ligand will unearth a huge number of new polymetallic clusters. For example, one only has to compare the Mn complexes of H4TBC [4] with those formed with H8TBC [8] to identify an area worthy of further investigation. Indeed, a systematic study of the entire 3d series is warranted. Such studies would ideally afford a set of empirical ion binding rules akin to those for H4TBC [4] that, once in hand, could potentially be used to target hetero-calixarene assemblies, i.e. systems supported by both ligand types that display their own structural preferences. Inspection of the clusters reported herein already delivers some structural trends, e.g. a tendency towards dimers, butterflies and octahedra. Figures S19-24 collect all the metallic skeletons of the polymetallic complexes reported herein for comparison. Formation of the very large Ln18 cluster suggests that it may be possible to access even larger assemblies that conform to highly symmetric solids capped by TBC [8]s in the double-cone conformation; this would be a direct extension from the well-documented structure-capping behaviour of TBC [4].