A bis-phenolate that has structural similarities to both calix[4]arene and the oxacalix[n]arenes provides access to a "butterfly"-like Mn 4 cluster in which all metals are in the oxidation state + 3. Specific properties of this ligand, in comparison to others in the literature, offer a route to influencing the orientation of the Jahn-Teller axes within this cluster motif, which possesses a rare oxidation state arrangement.Methylene-bridged calix[n]arenes are cyclic polyphenols that have emerged as excellent platforms for the synthesis of new polynuclear transition-metal (TM) and lanthanide (Ln) clusters. [1,2] We have explored this chemistry extensively with ptert-butyl-calix[4]arene/calix[4]arene (TBC[4]/C[4]) in particular and have reported a range of novel cluster motifs including: 1) [] This study has allowed us to establish a set of metal-ion binding rules for the general C[4] framework, and perhaps the most important feature of this is that the polyphenolic pocket shows strong affinity for Mn III ions in competition experiments. The metallic skeleton in the [Mn III 2 Mn II 2 (TBC[4]) 2 ] SMMs mentioned above describes a planar diamond or butterfly-like topology in which the wing-tip manganese ions (within the C[4] cavity) are in the oxidation state + 3, and the body manganese ions are in the oxidation state + 2 (Figure 1). These ions are linked by two m 3 -OH À ions located in the centre of the diamond forming a [Mn III 2 Mn II 2 (OH) 2 ] 8 + core. The four positions around the equatorial plane of each wing-tip Mn III ion are occupied by the oxygen atoms of a TBC[4] support, and in each case two of these m-bridge to the central Mn II ions. The remaining positions around all of the Mn II /Mn III ions are occupied by ligated dimethylformamide (DMF) molecules and the Jahn-Teller axes of the cavity-bound (and distorted octahedral) Mn III ions are defined by the O(DMF)-Mn-O(m 3 -OH À ) vector.A search of the Cambridge Structural Database (CSD) for clusters with a general Mn 4 O 6 core (Scheme 1 A) with no specific oxidation state distributions returned a total of 66 entries. [3] Analysis revealed a number of interesting trends. The first is that the vast majority of these have the opposite oxidation state distribution to that found in the [Mn III 2 Mn II 2 (TBC[4]) 2 ] SMM, that is, the wing-tip and body ions of the butterfly are Mn II and Mn III , respectively. [4] Six clusters have an arrangement in which wing-tip and body Mn ions are all in the oxidation state + 3, five of which are formed from reactions with ligands containing salicylideneamino moieties (see Scheme 1 B). [5][6][7] The final trend we observed is that, within our search for the general Mn 4 O 6 fragment/core, ligands containing phenol and ortho-methanol moieties bind Mn III ions with the Jahn-Teller axes oriented orthogonal to the near-planar ligand fragment (Scheme 1 C). [8] We recently began to investigate TM and Ln cluster formation with bis(5-tert-butyl-2-hydroxy-3-hydroxymethylphenyl)methane (H 4 L1, Figure 2 A) as it bears a striking [a]...