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

Abstract

Extension of previous work on the lanthanide(III) ion complexes of p-tert-butyltetrathiacalix [4]arene has led to a variety of structurally characterised species containing oxo-, hydroxo-and aqua-ligands presumably derived from water present in the preparative medium, along with the thiacalixarene in various stages of deprotonation. The overall stoichiometry of some species is remarkably complicated due to the presence of simple anions and multiple solvents. Simplest is the binuclear complex [(µ-H 2 O){Ln(O-dmf) 2 } 2 (HL·dmf) 2 ]·nS (dmf = dimethylformamide) [1Ln, Ln = Sm (nS = 2dmf), Eu (nS = 1.5dmf·2MeCN)], also the best-defined of all the arrays studied. The heaviest lanthanides give trinuclear Ln(OH) 3 · 2Ln(LH)·xdmf·yH 2 O (2Ln, Ln = Yb, Lu), while both oxo and hydroxo species are isolable with Eu: trinuclear Eu 3 O(L)-(LH)(LH 4 )·13dmf (3) and tetranuclear Eu 4 O(OH) 2 (L)(LH 2 ) 2 -(LH 4 )·12dmf (9), both somewhat atypical species containing uncoordinated thiacalixarene molecules within the lattice. Anion (NO 3 , ClO 4 ) coordination, as in the tri-and tetranuclear species, 4-6Ln, 9, 10Ln, 11Ln, 12, seems especially fav-

Systematic Structural Coordination Chemistry ofp‐tert‐Butyltetrathiacalix[4]arene: Main Group Metal Complexes Other Than Those of Group 1

“…In both the present and associated work, [52,53] it was commonly found, as for published cases, [30,[36][37][38][39][42][43][44] that the complexes could be formed readily by reaction of a solvated metal salt such as [M(dmso) n ](ClO 4 ) x in a dipolar, aprotic solvent (such as dimethyl sulfoxide, dmso) with a solution of the thiacalix [4]arene [LH 4 , prepared as in the literature [18] as its chloroform solvate, (LH 4 ·CHCl 3 )] and triethylamine in the same solvent (though other methods are known [28] ). Sometimes, this led only to the crystallisation of the triethylammonium derivative of the calixarene monoanion.…”

“…In total, this has allowed us to establish a considerable body of structural information, the significance of which we analyse further in the final part of this work, [53] in order to take as broad a context as possible. Thus, as intermediate conclusions, we note that the present report establishes four structures for group 2 metal ion [Ca(ϫ 2),Ba(ϫ 2)] complexes, three for group 13 metal ions [Ga, In(ϫ 2)] and one for a group 14 metal ion (Pb II ).…”

“…A number of intriguing features are nonetheless apparent in the results available, this paper expanding upon known studies of main group 1 cation complexes of both the partly deprotonated thiacalixarene (Part I) [37] and its fully deprotonated form, [51] to encompass further adducts with ions of main groups 2, 13 and 14, for which no structurally defined examples are yet known. In the present and its associated works concerned with transition metal [52] and lanthanide(III) [53] cation complexes, inclusion of a solvent molecule within a calixarene cavity is designated by the use of a large dot, "·", the parent fully protonated neutral ligand ( Figure 1) being LH 4 . Figure 1.…”

“…[52] ; part IV: ref. [53] [a] Chemistry M313, School of Biomedical, Biomolecular and Chemical Sciences, University of Western Australia, Crawley, Western Australia 6009 [b] cyclic ring atoms may be donors. Nonetheless, there are reasons to believe that the thiacalixarenes and their derivatives may constitute a rather unique class of macrocycles [21,27] with unusual metal-binding properties.…”

Supramolecular Assembly of <i>p</i>-Sulfonatothiacalix[6]arene Yttrium Complex Supported by Hydrogen Bonding, π–π Stacking, and S–π Interactions

“…In addition, both molecules 1 and 2 also provide fascinating assemblies such as 'molecular-capsule' and 'Ferriswheel' arrangements, which are formed when these lanthanide crown ethers complex with 2. Thiacalix[n]arenes (n = 4, 6, and 8) are interesting macrocyclic molecules and have a high affinity towards alkali [28][29][30][31][32][33], transition [34][35][36][37], and lanthanide [38][39][40] metal cations. Their ability to act as multidentate ligands can be explained by the formation of strong dative bonds between the empty d-orbitals on the metal and the lone pairs on the sulfur atoms bridging the phenol moieties.…”