210706-03-9Relevant articles and documents
Di- and tetracarboxylate ligands for highly luminescent terbium(III) complexes on the basis of sulfonylcalix[4]arene scaffold
Horiuchi, Takayuki,Iki, Nobuhiko,Hoshino, Hitoshi,Kabuto, Chizuko,Miyano, Sotaro
, p. 821 - 825 (2007)
New di- (2) and tetracarboxylate ligands (4) were prepared on a sulfonylcalix[4]arene platform by O-alkylation of thiacalix[4]arene with ethyl bromoacetate, followed by hydrolysis of the ester function and oxidation of the sulfide bridges. The sulfonyl-based ligands 2 and 4 formed luminescent 1:1 complexes with terbium(III) ion having higher luminescent quantum yield (Φ = 0.291 and 0.287, respectively) than 1:1 complexes of the corresponding thiacalix[4]arene-based di- (1) and tetracarboxylate ligands (3) (Φ = 0.038 and 0.003, respectively), implying higher efficiency of sulfonyl ligands (2 and 4) than those of thia ligands (1 and 3) in the energy transfer process.
Geometric change of a thiacalix[4]arene supramolecular gel with volatile gases and its chromogenic detection for rapid analysis
Kim, Ka Young,Park, Sunhong,Jung, Sung Ho,Lee, Shim Sung,Park, Ki-Min,Shinkai, Seiji,Jung, Jong Hwa
, p. 3004 - 3011 (2014)
A coordination polymer gel that is self-assembled to form a network structure between a thiacalix[4]arene derivative (L) and Co2+ has been prepared. This gel is capable of selectively changing color in the presence of gases that yield hydrogen chloride upon hydrolysis. The UV-vis absorption spectrum of a coordination polymer gel derived from Co(NO3) 2 exhibits an absorption band at 527 nm and is colored red, indicating the formation of an octahedral Co2+ complex. Treatment with a small amount of volatile gases containing a chlorine atom (VGCl) causes a red shift of ～150 nm, resulting in a new strong band with a maximum at 670 nm and a color change to blue. In addition, the red color of the filter paper coated with a Co(NO3)2 coordination polymer gel changed to blue upon exposure to VGCl, reflecting a change in the coordination geometry. Red and blue colors of single crystals of Co2+ complexes were obtained from a basic solution. From X-ray crystallographic analysis, the red Co2+ complex corresponds to an octahedral structure, while the blue Co2+ complex reflects the presence of a tetrahedral structure. Thus, the induced color change of Co2+ gel from red to blue upon exposure to VGCl is due to the coordination geometry. The quantitative concentration of VGCl was calculated by employing the RGB histogram available in a smartphone application.
Complexation of GdIII with tetra-p-tert-butylthiacalix[4]arenoic acid in micellar media
Amirov,Ziyatdinova,Burilova,Zhukov,Antipin,Stoikov
, p. 1400 - 1407 (2009)
The conditions for the formation of gadolinium(III) complexes possessing high relaxivity with various tetraacid stereoisomers based on p-tert-butylthiacalix[4]arene in micellar solutions of nonionic surfactants were established. The acid-base properties of individual isomers of the ligand were studied by pH-metric titration and UV spectroscopy. The composition and stability constants of the solubilized gadolinium(III) complexes with the obtained thiacalixarenes were determined using computer simulation of the NMR relaxation data.
Aminolysis of p-tert-butyltetrathiacalix[4]arene tetraethylacetates in cone, partial cone and 1,3-alternate conformation: synthesis of amide based receptors for oxyanions
Singh, Suneel Pratap,Chakrabarti, Ananya,Chawla, Har Mohindra,Pant, Nalin
, p. 1983 - 1997 (2008)
Cone, partial cone and 1,3-alternate conformers of tetrathiacalix[4]arene tetraethylacetate were synthesized and subjected to aminolysis with alkyl amines [CH3(CH2)nNH2; n=2, 3, 5] to yield mono-, di-, tri- or tetrasubstituted p-tert-butyltetrathiacalix[4]arene amides which were characterized by detailed analysis of their NMR spectral and single crystal X-ray crystallography. It has been observed that while the 1,3-alternate and cone conformers of the tetrathiacalix[4]arene tetraethylacetate gave corresponding tetrathiacalix[4]arene tetraamides under different experimental conditions, the corresponding partial cone conformer undergoes a cascade of regioselective reactions with the same amines. Variable temperature 1H NMR experiments allowed the determination of relative stability of different conformers within the temperature range of 298-333 K. The synthesized derivatives were evaluated as molecular extractants for cations and anions and were determined to facilitate extraction of oxyanions (CrO42- and Cr2O72-) from aqueous to the organic phase. The studies have a significance in the design of tetrathiacalix[n]arene based molecular receptors for innovative applications.
Catechol-containing schiff bases on thiacalixarene: Synthesis, copper (ii) recognition, and formation of organic-inorganic copper-based materials
Arsenyev, Maxim,Baryshnikova, Svetlana,Boldyrev, Artur,Gerasimov, Alexander,Grishaev, Denis,Khannanov, Artur,Padnya, Pavel,Shiabiev, Igor,Shibaeva, Ksenia,Shtyrlin, Yurii,Stoikov, Ivan,Terenteva, Olga
, (2021)
For the first time, a series of catechol-containing Schiff bases, tetrasubstituted at the lower rim thiacalix[4]arene derivatives in three stereoisomeric forms, cone, partial cone, and 1,3-alternate, were synthesized. The structure of the obtained compoun
Synthesis and 1H NMR complexation study of thiacalix[4]arene tetraacetates
Lhotak, Pavel,Stastny, Vaclav,Zlatuskova, Petra,Stibor, Ivan,Michlova, Veronika,Tkadlecova, Marcela,Havlicek, Jaroslav,Sykora, Jan
, p. 757 - 771 (2000)
Alkylation of thiacalix[4]arenes with ethyl bromoacetate led to high yields (≈60%) of corresponding tetraacetates in various conformations (cone, partial cone, 1,3-alternate) depending strictly on the carbonate (Na, K, Cs) used for the reaction. The complexation ability of new compounds was studied by 1H NMR.
Selective synthesis of three conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]thiacalix[4]arene and their complexation properties towards alkali metal ions
Iki, Nobuhiko,Narumi, Fumitaka,Fujimoto, Toyohisa,Morohashi, Naoya,Miyano, Sotaro
, p. 2745 - 2750 (1998)
5,11,17,23-Tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene-25,26,27,28- tetrol (TCA) underwent facile tetra-O-alkylation by treatment with ethyl bromoacetate in the presence of an alkali carbonate as base catalyst in DMF or acetone to provide a mixture of conformational isomers (cone, partial cone, and 1,3-alternate) of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-2,8, 14,20-tetrathiacalix[4]arene(1), the stereochemistries of which were unambiguously assigned by 1H NMR and X-ray analysis. The isomer distribution depended significantly on the base used, thus providing a facile route for the preparation of a particular conformer; Na2CO3, K2CO3, and Cs2CO3 gave cone- (77% yield), partial-cone- (58% yield), and 1,3-alternate-1 (78% yield) in acetone, respectively. Cone- and partial-cone-1, in turn, showed preference for Na+ and K+, respectively, in an ion-pair extraction study, while 1,3-alternate-1 preferred most Rb+ ion, followed by K+ and then Cs+. These results imply that the size of the cavities provided by the (ethoxycarbonyl)methoxy groups arranged on the periphery of the thiacalix[4]arene skeleton is in the order cone- + ion was determined to be 1:1 with the stability constant of 102.85 mol-1 dm3 in 50 (v/v)% CDCl3-CD3OD.
Synthesis of multivalent oxamate ligands based on calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation
Noamane, Mohamed Habib,Ferlay, Sylvie,Abidi, Rym,Hosseini, Mir Wais
, p. 4259 - 4264 (2017)
Five new multivalent ligands based on either p-tert-butylthiacalix[4]arene (TCA) 1 or p-tert-butylcalix[4]arene (CA) 2 backbones in 1,3-Alternate conformation bearing four oxamate coordinating groups at their lower rim were designed and synthesized by a multistep strategy. These ligands differ either by the nature of the calix[4]arene backbone (CA or TCA) or by the nature of the spacer ((CH2)n) connecting the oxamate binding units to the backbone.
New bifunctional compounds obtained by selective hydrolysis of tetrathiacalix[4]arene tetraethyl esters with Cs2CO3
Podyachev, Sergey N.,Sudakova, Svetlana N.,Gabidullin, Bulat M.,Syakaev, Victor V.,Gubaidullin, Aidar T.,Dehaen, Wim,Konovalov, Alexander I.
, p. 3135 - 3139 (2012)
A new strategy for the synthesis of bifunctional compounds, based on 1,3-alternate tetrathiacalix[4]arene precursors functionalized by pairs of carboxylic acid and ester groups located on opposite sides of the macrocycle platform is described. These building blocks were prepared by the Cs 2CO3 induced selective hydrolysis of tetrathiacalix[4] arene tetraester derivatives. A mechanism for the selective hydrolysis is suggested. The structures of the compounds are elucidated by NMR spectroscopic analysis and X-ray single crystal diffraction.
Synthesis of conformationally diverse tetrathiacalix[4]arene(amido)crowns and tetrathiacalix[4]arene amides with pendant amine functions
Chakrabarti, Ananya,Chawla,Pant,Singh, Suneel Pratap,Upreti
, p. 8974 - 8981 (2006)
A series of conformationally diverse novel tetrathiacalix[4]arene(amido)crowns and amides from tetrakis((ethoxycarbonyl)methoxy)p-tert-butyl tetrathiacalix[4]arene and its debutylated analog have been prepared by their reaction with diamines [H2N(CH2)nNH2; n=2,3,4, and 6] and polyamines. It has been determined that the length of the alkyl spacer in diamines is pivotal for the formation of either the tetrathiacalix[4]arene bis(amido)crowns or tetrathiacalix[4]arene amides with pendant amine functions. The synthesized compounds represent potential building blocks for achieving sophisticated molecular assemblies for molecular organization and recognition. Single crystal X-ray analysis of tetrathiacalix[4]arene bis(amido)crown 6a revealed that it has a 1,3-alternate conformation, which forms supramolecular complexes with chloroform.
