A {Co₃₂} Nanosphere Supported by p-tert-Butylthiacalix[4]arene

Abstract

Calixarene-capped Co(32) clusters are constructed by a sodalite Co(II)(24) cage and an encapsulated Co(III)(8) cube. The spherical units are arranged into three isomeric structures, two of which are stacked by the bcc lattices and the third of which is assembled by the cubic closest packing of the spherical units.

Systematic Structural Coordination Chemistry of p‐tert‐Butyltetrathiacalix[4]arene: Further Complexes of Transition‐Metal Ions

“…36 ]·MeCN, [42] though quite unlike that of a hydrolytic Ga 32 array. [43] The structure is closely related to that of the recently reported [44] Co 32 (thiacalix [4]arene) 6 complex, although that appears to contain both Co II and Co III centres, whereas the present complex appears to contain only Ni II . The Co complex was prepared by a solvothermal method (at 130°C), which has the obvious advantage of rapid kinetics compared to the procedure we have used to obtain the Ni complex but this may also have led to the partial oxidation and extensive hydrolysis, explaining why a much simpler true Co II complex was obtained in our earlier work.…”

“…[17] It should be noted, however, that for the transition metals (and lanthanides) there is a considerable body of work concerning complexes of thiacalixarene derivatives, [2] and that this and past and present work with p-tert-butyltetrathiacalix [4]arene justify the conclusion that both thiacalixarene and calixarene ligands should be considered as "cluster keepers" [1] for metal ions. The Ni 32 species presently described and its Co 32 analogue [44] provide spectacular illustration of the capacity of the unfunctionalised ligand to provide larger cluster species than do its derivatives. Other notable particular features of the complexes presently studied are the marked conformational distortions seen in the W VI and mixed Pd II /Ca II complexes and the fact that this seems to preclude solvent inclusion, which is otherwise the norm in complexes where the thiacalixarene has a close-to-regular cone conformation.…”

A Family of Calix[4]arene‐Supported [MnIII2MnII2] Clusters

“…[8] Phenol, biphenols and other bi-, tri-and polyols have proven to be tremendously successful ligands in cluster synthesis, [9] and in this regard thia-and sulfonyl-bridged calix [4]arenes [10] have been widely exploited for this purpose. This is predominantly due to the fact that the S, SO or SO 2 groups can heavily influence the resulting coordination chemistry.…”

A Calix[4]arene 3d/4f Magnetic Cooler

“…[11] Thiacalix [4]arenes and their oxidized derivatives 2-4 ( Figure 1 b) possess additional donor atoms, and these have been used in the formation of a number of polynuclear transition-metal or Ln clusters. [12,13] The additional donor atoms (relative to 1) around the molecular skeleton play a key role in supporting complex formation by taking part in the bonding within the metal-cluster framework.…”