Synthesis and structures of O-anthrylmethyl-substituted hexahomotrioxacalix[3]arenes

O-Alkylation of 7,15,23-tri-tert-butyl-25,26,27-trihydroxy-2,3,10,11,18,19-hexahomo-3,11,19-trioxacalix[3]arene (1H₃) with 9-chloromethylanthracene 5 was carried out under different reaction conditions. Variation of the number of anthrylmethyl group introduced at the phenolic rim of hexahomotrioxacalix[3]arene 1H₃ was achieved through selective O-alkylation using stoichiometric amounts of 9-chloromethylanthracene 5 in acetone to afford the mono-O-alkylated product 2H₂An, the di-O-alkylated product 3HAn₂ and the tri-O-alkylated product partial-cone-4An₃, respectively. Interestingly, by using an acetone/benzene (1:1 v/v) mixed solvent system, the cone-4An₃ was successfully synthesized. These results suggest that the solvent can also control the conformation of the O-alkylation products. The possible reaction routes of the cone-4An₃ and partial-cone-4An₃ are also discussed

A study of allosteric binding behaviour of a 1,3-alternate thiacalix[4]arene-based receptor using fluorescence signal

A novel heteroditopic thiacalix[4]arene receptor L possessing 1,3-alternate conformation, which contains two pyrene moieties attached to the lower rim via urea linkages together with a crown ether moiety appended at the opposite side of the thiacalix[4]arene cavity, has been synthesized. The complexation behaviour of receptor L was studied by means of fluorescence spectra and ¹H NMR titration experiments in the presence of K⁺ ions and a variety of other anions. The results suggested that receptor L can complex efficiently via the urea cavity or the crown ether moiety, and a positive/negative allosteric effect operating in receptor L was observed

Positive allosteric binding behavior of pyrene-appended triazole-modified thiacalix[4]arene-based fluorescent receptors

The novel heteroditopic receptors 5a∼c have been synthesized, which bear a thiacalix[4]arene in the 1,3-alternate conformation. Two urea moieties possessing various aryl groups with either electron-donating or -withdrawing groups at their p-positions function as anion-binding sites. At the opposite side of the cavity are two pyrene-appended triazole rings, which act as cation-binding sites. The binding property of receptor 5c was investigated by means of 1H NMR and UV–vis spectroscopy and by fluorescence titration experiments in the presence of various transition metal cations and anions in CH2Cl2–DMSO (10:1, v/v) solution. Interestingly, it was found that receptor 5c possessing two p-nitrophenyl ureido moieties, most efficiently complexes in the urea cavity or bistriazoles; the plausible allosteric effect of receptor 5c was also investigated

Synthesis and inclusion behavior of a heterotritopic receptor based on hexahomotrioxacalix[3]arene

A heterotritopic hexahomotrioxacalix[3]arene receptor with the capability of binding two alkali metals and a transition metal in a cooperative fashion was synthesized. The binding model was investigated by using ¹H NMR titration experiments in CDCl₃–CD₃CN (10:1, v/v), and the results revealed that the transition metal was bound at the upper rim and the alkali metals at the lower and upper rims. Interestingly, the alkali metal ions Li⁺ and Na⁺ bind at the lower and upper rim respectively depending on the dimensions of the alkali metal ions versus the size of the cavities formed by the calix[3]arene derivative. The hexahomotrioxacalix[3]arene receptor acts as a heterotritopic receptor, binding with the transition metal ion Ag⁺ and the alkali metals ions Li⁺ and Na⁺. These findings were not applicable to other different sized alkali metals, such as K⁺ and Cs⁺

A pyrene-armed hexahomotrioxacalix[3]arene as a multi-sensor via synergistic and demetallation effects

A new pyrene-armed hexahomotrioxacalix[3]arene L has been synthesized, which exhibits a pronounced fluorescence enhancement response toward Cu²⁺ ions via a Zn²⁺ or Cd²⁺ triggered synergistic effect. Additionally, the L·Cu²⁺+ complex can subsequently serve as a sensor for F⁻ via anion-induced demetallation. The fluorescence responses by the input of Cu²⁺, Zn²⁺/Cd²⁺ and F⁻ can be constructed as a combinational logic gate which mimics a set of molecular traffic signals

A pyrene-functionalized triazole-linked hexahomotrioxacalix[3]arene as a fluorescent chemosensor for Zn²⁺ ions

A new pyrenyl appended hexahomotrioxacalix[3]arene L featuring 1,2,3-triazole linkers was synthesized as a fluorescent chemosensor for Zn²⁺ in mixed aqueous media. It exhibited high affinity toward Zn²⁺, and the monomer and excimer emission of the pyrene moieties could be adjusted. The binding stoichiometry of the L·Zn²⁺ complex was determined to be 1:1, and the association constant (Ka) was found to be 7.05 × 10⁴ M⁻¹. The binding behavior with Zn²⁺ has been confirmed by ¹H NMR spectroscopic analysis

Fluorescent turn-on sensors based on pyrene-containing Schiff base derivatives for Cu2+ recognition: spectroscopic and DFT computational studies

A new fluorescent chemosensor L1, pyrene containing long chain Schiff base derivative in 1-position has been synthesized. Similarly, the receptors L2 and L3 are also designed in order to compare the binding ability for detection of Cu2+. The receptors exhibit very weak fluorescence (Φ = 0.01) due to the photoinduced electron transfer (PET). Upon addition of 10 equiv. of Cu2+, the emission intensity of ligands L1 and L2 are increased 65-fold (Φ = 0.31) and 25-fold (Φ = 0.08) in CH3CN/CH2Cl2 solvents system respectively. NMR titration experiments, spectroscopic and DFT computational studies confirmed the binding phenomena and sensitivity of Cu2+

Synthesis and evaluation of a novel fluorescent sensor based on hexahomotrioxacalix[3]arene for Zn²+ and Cd²+

A novel type of selective and sensitive fluorescent sensor having triazole rings as the binding sites on the lower rim of a hexahomotrioxacalix[3]arene scaffold in a cone conformation is reported. This sensor has desirable properties for practical applications, including selectivity for detecting Zn²⁺ and Cd²⁺ in the presence of excess competing metal ions at low ion concentration or as a fluorescence enhancement type chemosensor due to the cavity of calixarene changing from a ‘flattened-cone’ to a more-upright form and inhibition of PET. In contrast, the results suggested that receptor 1 is highly sensitive and selective for Cu²⁺ and Fe³⁺ as a fluorescence quenching type chemosensor due to the photoinduced electron transfer (PET) or heavy atom effect

Synthesis and evaluation of a novel ionophore based on a thiacalix[4]arene derivative bearing imidazole units

O-Alkylation of the flexible thiacalix[4]arene 1 with 2-chloromethyl-1-methyl-1H-imidazole 2 in the presence of Na₂CO₃ or K₂CO₃ afforded mono-O-alkylation product 3 in 29–51% yield, along with recovery of the starting compound. In contrast, the same reaction in the presence of Cs₂CO₃ gave only one pure stereoisomer, namely 1,3-alternate-4; other possible isomers were not observed. Alkali metal salts such as Na₂CO₃ and Cs₂CO₃ can play an important role in the conformer distribution via a template effect. The conformations of the receptors, mono-O-alkylation product 3 and that of 1,3-alternate-4, have been confirmed by X-ray crystallography. Furthermore, the complexation properties of the receptor 1,3-alternate-4 toward selected alkali/transition metal cations are reported. The two-phase solvent extraction data indicated that 1,3-alternate-4 exhibited a stronger extraction efficiency for transition metals over alkali metals. The dichromate anion extraction ability of 1,3-alternate-4 showed that it could serve as an efficient extractor of HCr₂O₇⁻/Cr₂O₇²⁻ anions at low pH

Click-modified hexahomotrioxacalix[3]arenes as fluorometric and colorimetric dual-modal chemosensors for 2,4,6-trinitrophenol

A new type of chemosensor-based approach to the detection of 2,4,6-trinitrophenol (TNP) is described in this paper. Two hexahomotrioxacalix[3]arene-based chemosensors 1 and 2 were synthesized through click chemistry, which exhibited high binding affinity and selectivity toward TNP as evidenced by UV–vis and fluorescence spectroscopy studies. ¹H NMR titration analysis verified that CH⋯O hydrogen bonding is demonstrated as the mode of interaction, which possibly facilitates effective charge-transfer