ABSTRACT
A fluorogenic derivative of 1,3-alternate calix[4]arenebis(crown-6) (1) containing a dansyl group in the proton-ionizable side arm has been employed in selective sensing of Tl+ and Cs+ at low concentration levels in MeCN-H2O (1:1) mixed solvent. Optical recognition of these two metal cations by 1 occurs in contrasting modes. On the basis of the results of fluorescence, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), and 1H NMR studies, Tl+ and Cs+ react with 1 via formation of 1:1 complexes that differ in coordination arrangement around the metal ion.
Subject(s)
Cesium/analysis , Crown Ethers/chemistry , Fluorescent Dyes/chemistry , Microscopy, Fluorescence/methods , Optics and Photonics , Thallium/analysis , Cations/analysis , Magnetic Resonance Spectroscopy , Phosphatidylcholines/chemistry , Spectrometry, Mass, Matrix-Assisted Laser Desorption-IonizationABSTRACT
A metal-organic framework with one-dimensional channels decorated with -COOH binding sites was synthesized under aqueous acidic conditions, which inhibited the participation of these groups to metal coordination or self-association by hydrogen bonding. This material selectively includes Cl(H2O)4- clusters in its channels, as revealed by single-crystal X-ray diffraction analysis, which represents the first structural characterization of such a water-chloride cluster.
ABSTRACT
A new fluorogenic, dansyl group-containing derivative of 1,3-alternate calix[4]arene-bis(crown-6-ether) provides optical recognition of Tl+ with selectivity over many other metal cations, including Na+, K+, Ca2+, Ag+, Hg2+ and Pb2+, and embodies the first example of a calixarene-based fluorescent Tl+-chemosensor.
Subject(s)
Calixarenes/chemistry , Crown Ethers/chemistry , Fluorescent Dyes/chemistry , Thallium/chemistry , Molecular StructureABSTRACT
Hydrogen bonding in crystalline N,N'-dialkylthioureas was examined with the help of single-crystal X-ray diffraction, DFT calculations, and Cambridge Structural Database (CSD) analysis. A CSD survey indicated that unlike the related urea derivatives, which persistently self-assemble into one-dimensional hydrogen-bonded chains, the analogous thioureas can form two different hydrogen-bonding motifs in the solid state: chains, structurally similar with those found in ureas, and dimers, that further associate into hydrogen-bonded layers. The formation of one motif or another can be manipulated by the bulkiness of the organic substituents on the thiourea group, which provides a clear example of steric control over the hydrogen bonding arrangement in crystalline organic solids.