Tb(III) complexes with nonyl-substituted calix[4]arenes as building blocks of hydrophilic luminescent mixed polydiacetylene-based aggregates (original) (raw)
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New Journal of Chemistry, 2014
The work presents the synthesis of a novel calix[4]resorcinarene cavitand bearing four 1,3-diketone groups at the upper rim and its complex formation with Tb(III) ions in DMF and DMSO solutions. Electrospray ionization mass spectra, 1 H NMR, UV-Vis and luminescence spectra indicate a long (three hours at least) equilibration time for the complex formation between the cavitand and Tb(III) in alkaline DMF and DMSO solutions. These results are explained by the restricted keto-enol conversion, resulting from the steric hindrance effect of the methylenedioxy-groups linking the benzene rings within the cavitand framework.
Croatica Chemica Acta, 2017
Two novel fluorescent calix[4]arenes comprising diphenylanthracene moiety at the lower rim were synthetized and their complexation with alkali metal cations in acetonitrile/dichloromethane and methanol/dichloromethane mixtures (φ = 0.5) was studied experimentally and by classical molecular dynamics and quantum chemical calculations. The monosubstituted calixarene derivative (L1) proved to be a poor cation receptor, whereas the ester-based macrocycle (L2) exhibited rather high affinity towards lithium, sodium and potassium cations, particularly in MeCN/CH2Cl2. All complexation reactions were enthalpically controlled, whereby the overall stability was the largest in the case of sodium complex. The computational investigations provided an additional insight into the complexation properties and structures of complex species. The molecular dynamics simulations indicated the occurrence of inclusion of solvent molecules in the calixarene hydrophobic cavity of the free and complexed ligand, which was found to significantly affect the complexation equilibria.
European Journal of Inorganic Chemistry, 1998
] 3+ , respectively} and high metal luminescence quantum yields {Φ = 0.19 and 0.11 for [Eu(1)] 3+ and [Eu(2)] 3+ , cone-shaped podand 1 and the barrel-shaped cryptand 2, based on calix[4]arenes incorporating bipyridine N,NЈ-respectively} were obtained. The effect of OH oscillators, attached at the lower rim of the calixarenes, on the non-dioxide chromophores, have been synthesized and characterized. The complexes were found to be stable in radiative deactivation to the ground state has been demonstrated. water and coordinating solvents. High molar absorption coefficients {ε = 28000 and 36000 M -1 cm -1 for [Eu(1)] 3+ and
Journal of Solid State Chemistry, 2017
Lanthanide-calixarene hybrid materials are of particular interest due to the combination of the interesting properties of the ligand cavity-like structure and the luminescent features of lanthanides. The aim of this study was to synthesize and investigate the photophysical properties of Eu 3+ , Tb 3+ and Gd 3+ hybrids based on calix[4] arene-tetracarboxylate. The preparation of two structurally different Tb 3+ compounds (calix-TA-SC-Tb and calix-TA-Tb) was dictated by the ligand to metal molar ratio and the synthesis time. Analysis of calix-TA-SC-Tb monocrystals revealed the formation of a mononuclear complex of C 2 symmetry containing Tb 3+ coordinated by four calixarene ionized groups and formate anion encapsulated within the upper cavity. Syntheses of other hybrids failed in producing high-quality crystals and the structures could not be solved. The solid-state luminescent properties of hybrids were evaluated, and the structure/property relationship was investigated. Based on the emission and excitation spectra, the energy diagrams for calix-TA-Eu, calix-TA-Tb and calix-TA-Gd were proposed.
Water-Soluble Neutral Calix[4]arene−Lanthanide Complexes: Synthesis and Luminescence Properties
The Journal of Organic Chemistry, 1997
Water-soluble calix[4]arenes 10a,b with chromophores ("antenna") attached to the lower rim via a short spacer are described. In the neutral lanthanide complexes of 10a,b photoexcitation of the antenna induces lanthanide emission via intramolecular energy transfer. Calix[4]arene 10b with a chrysene moiety as sensitizer shows strong lanthanide emission for Eu 3+ with an excitation maximum at λ) 363 nm.