Second-sphere coordination in the complex [Mn(H2O)6]2[thiacalix[4]arene tetrasulfonate]

Outer-Sphere Association of p-Sulfonatothiacalix[4]arene and Tetrasulfonatomethylated Calix[4]resorcinarene with Cobalt(III) Tris(dipyridyl): The Effect on the Spectral and Electrochemical Properties of the Latter

“…The inclusion mode of [Co(dipy) 3 ] 3+ in the cavity of 1 4 - is similar to that of 1 5 - which is in accordance with above mentioned 1 H NMR data in solutions. The up−down face to face π-stacking interaction between the inclusion complexes of p -sulfonatothiacalix[4]arene units very often provides a so-called bilayer supramolecular structure. − The assembly of the inclusion complexes of 1 4 - with [Co(dipy) 3 ] 3+ results in a tubular superstructure, which is unlike the tubular structure of the assembly of p -sulfonatocalix[4]arene inclusion complexes, provided by the up−up arrangement of calixarene units. It is also interesting to note that, unlike the [Ni(dipy) 3 ] 2+ − p -sulfonatocalix[4]arene system 13 in which the presence of the equilibrium mixture of tetra- and penta-anions results in a crystal structure with both tetra- and penta-anions, the system of [Co(dipy) 3 ] 3+ and 1 has two different crystal structures which are dependent on the form of 1 ( 1 4 - and 1 5 - ).…”

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

“…S (23,24), with associated C-S-C angles closely akin to those at the coordinated [range, C-S-C (ligand 2) 101.6 (1) (Table S1). …”

“…[16] ; part IV: ref. [17] [a] Chemistry M313 40 (L) 6 · 8dmso·10dmf, in which there are two sets of nickel atoms, one disposed at the corners of a cube (Ni 8 ), the other (Ni 24 ) at the vertices of a cuboctahedron (the Ni 8 vertices at the centres of the hexagonal faces); the hydroxy groups comprise two sets: one, (OH) 24 , disposed outside the spheroidal shell of nickel atoms, the other, (OH) 16 , disordered within, the thiacalixarene ligands L 6 with only partial success in terms of obtaining crystalline materials suitable for diffraction studies. While there is evidence, elaborated on in the associated present reports [16,17] of more general thiacalixarene coordination chemistry, that the nature of the complex which crystallises from a given synthetic mixture may be subject to somewhat capricious influences, other recent work [5b,12,13] has shown that solvothermal syntheses appear to have good reproducibility and that this method may enable access to a more complete definition of at least the solid state coordination chemistry of transition-metal ion complexes of the thiacalixarene.…”

Chemistry of Thiacalixarenes

“…[64] The resulting sulfonate 62a was isolated as the tetrasodium salt in 69 % yield. The single-crystal X-ray structures of this tetrasodium salt [65] and the corresponding dimanganese complex [66] have recently been published. It is noteworthy that the tetrasulfonate 62c, which possesses four sulfone bridging groups (-SO 2 -) was prepared by ipso-sub- stitution of the corresponding tetrasulfone [67] using chlorosulfonic acid at 140°C (compare with the above-described ipso-nitration of thiacalix [4]arene).…”