Article

One-step heterogeneous assembly of terbium(iii) and silver(i) with thiacalix[4]arene ligands to form a cage including terbium(iii) in an octa-oxygen cube

Journal of Inclusion Phenomena (Impact Factor: 1.43). 08/2009; 64(3):379-383. DOI: 10.1007/s10847-009-9567-0

ABSTRACT A heterogeneous one-step self-assembly of Ag+, Tb3+, and thiacalix[4]arene (TCAS), of which the donor atoms S and O showed high selectivity toward Ag+ and Tb3+ ions, respectively, afforded a supramolecular cage compound,

\textAg4 + \textTb 3+ \textTCAS 2 {\text{Ag}}_{4}^{ + } \cdot{\text{Tb}}^{ 3+ } \cdot{\text{TCAS}}_{ 2} , at the center of which an octa-oxygen cube encapsulated the Tb3+ center to completely shield it from solvent molecules.

0 Followers
 · 
122 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: This review article proposes a non-covalent strategy for activating separation and detection functionality; this strategy acts not through extensive organic synthesis to a covalently constructed molecular receptor, but by combining a simple molecular platform with a chemical “field” or functional component. For such a platform, we employed thiacalixarenes—calixarenes in which the bridging methylene groups are replaced with sulfur—to demonstrate usefulness of the non-covalent strategy and the multifunctionality of thiacalixarene. Thiacalixarene exhibits inherent abilities to recognize metal ions by coordinating with the bridging sulfur and adjacent phenol oxygen, as well as to include organic guest molecules in the cavity. Moreover, the non-covalent coupling of thiacalixarene provides systems with functions higher than thiacalixarene by itself. The functions described in this paper are as follows: (1) a 200-fold pre-concentration of heavy metal ions such as CuII, CdII, and PbII; (2) a pre-column derivatization reagent for the highly selective and sensitive determination of NiII, AlIII, FeIII, and TiIV at sub-ppb levels with reversed-phase HPLC; (3) the self-assembled formation of a luminescence receptor with TbIII ions for the detection of 10−10M levels of 1-ethylquinolinium guest; and (4) a sensing system for 10−9M levels of AgI ions by the formation of the AgI-TbIII-thiacalixarene ternary supramolecular complex. These examples support the non-covalent strategy as a highly promising way to obtain functions beyond that of a molecular platform. In addition, these diverse functions indicate the multifunctionality of thiacalixarene as well as its suitability to the non-covalent strategy, since the inherent functional groups—such as the bridging sulfur, phenol oxygen, p-substituent, aromatic ring, and hydrophobic cavity—synergistically perform the functions.
    Journal of Inclusion Phenomena 06/2009; 64(1):1-13. DOI:10.1007/s10847-009-9550-9 · 1.43 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: In extension of earlier work on complexes of p-tert-butyltetrathiacalix[4]arene, LH4, with late transition-metal MII species, we report studies of complexes modelled on the basis of single-crystal X-ray studies as derivatives of VV, WVI, MnII, FeIII, NiII, CuII and PdII, the last as a trio of heteronuclear species also involving CaII. In complexes [VO(OH)(LH2)·2.5dmf·2H2O] (×2) (1), Cl2W(L)·3.5C6H6 (2) and [Mn(LH2)·3.5CH2Cl2] (×2) (3) included dmf is found only in the partially deprotonated calixarene cavities of 1 and 3. In oligonuclear OFe3(HCO2)(LH)2·2H2O·6dmf (4) and 2Cuac2·Cu2(L)·dmf·4.5CH2Cl2 (6) (ac = acetate) included dmf is found in both. NiII provides several species, including 5a, binuclear (Et3NH)Ni2(LH)(LH2)·2dmf·2Me2CO·H2O, 5b, a remarkable hexanuclear (binuclear + tetranuclear) aggregate, Ni6(L)(LH)2(LH2)·4MeCN·6H2O, and 5c, an even more remarkable Ni32 aggregate modelled as (centrosymmetric) Ni32(OH)40(L)6·8dmso·10dmf, in which there are two sets of nickel atoms, one disposed at the corners of a cube (Ni8), the other (Ni24) at the vertices of a cuboctahedron (the Ni8 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 L6 being disposed about the axes of the octahedron. Heteronuclear species have been found as CaII/PdII combinations CaPd2(LH)2·1.5CH2Cl2 (7a), CaPd(LH2)·3dmso·H2O·4.5MeCN (7b), Ca2Pd(LH)2·3.5dmso·1.5H2O·4MeCN (7c), all with included solvent.
    Berichte der deutschen chemischen Gesellschaft 05/2010; 2010(14):2106 - 02126. DOI:10.1002/ejic.200901071
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Calixarenes, as nano-baskets, are considered an important group of macrocycles as the third famous host molecules after cyclodextrins Calixarenes, as nano-baskets, are considered an important group of macrocycles as the third famous host molecules after cyclodextrins and crown ethers have been subject to extensive researches in construction of many extractants, transporters, stationary phases, and crown ethers have been subject to extensive researches in construction of many extractants, transporters, stationary phases, electrode ionophores and optical and electrochemical sensors over the past four decades. Because of the recent rapid growth electrode ionophores and optical and electrochemical sensors over the past four decades. Because of the recent rapid growth in the publications of calixarene applications, this review paper has focused on different analytical applications of calixarenes in the publications of calixarene applications, this review paper has focused on different analytical applications of calixarenes in the main fields of separation, electroanalysis, spectroscopy and chemometrics. The objectives and the results of about in the main fields of separation, electroanalysis, spectroscopy and chemometrics. The objectives and the results of about 300 references mainly were published in recent 6years with emphasis on the analytical applications were reviewed. 300 references mainly were published in recent 6years with emphasis on the analytical applications were reviewed. KeywordsCalixarene–Complexation–Separation–Electroanalysis–Spectroscopy–Chemometrics KeywordsCalixarene–Complexation–Separation–Electroanalysis–Spectroscopy–Chemometrics
    Journal of Inclusion Phenomena 02/2011; 69(1):1-55. DOI:10.1007/s10847-010-9848-7 · 1.43 Impact Factor
Show more