Complexation and DFT studies of lower rim hexahomotrioxacalix[3]arene derivatives bearing pyridyl groups with transition and heavy metal cations. Cone versus partial cone conformation

Abstract

The binding of representative alkali, alkaline earth, transition and heavy metal cations by 2-pyridylmethoxy derivatives (1b, in cone and partial cone conformations) of p-tert-butylhexahomotrioxacalix[3]arene (1a) was assessed by spectrophotometry, microcalorimetry, proton NMR spectrometry and density functional theory methods

Toward Understanding of the Lower Rim Binding Preferences of Calix[4]arene

“…In addition to showing potential for use in the synthesis of single molecule magnets, the binding energy of numerous calixarenes toward a variety of heavy metals and group I/II metals has been investigated both experimentally and theoretically ,− leading to consideration of calixarenes as a scavenging agent in environments which have become polluted by such metals. We therefore present the results of a theoretical investigation into the binding preferences of calixarenes toward the entire first row of transition metals using C[4].…”

A pyrenyl-appended C-symmetric hexahomotrioxacalix[3]arene for selective fluorescence sensing of iodide

“…Importantly, homooxacalix [n]arenes incorporate extra ethereal linkages which makes them relatively flexible and thus they can provide a suitable binding environment for species that require trigonal-planar, tetrahedral, or octahedral coordination [24][25][26]. Based on this excellent structural versatility, homooxacalix[n]arenes exhibit characteristic affinities for metal cations [27,28], ammonium cations [29,30], anions [31,32] and fullerene derivatives [33,34]. However, homooxacalix [3]arenes has been scarcely exploited for the design of anions receptors.…”

TD-DFT Study on Thiacalix[4]arene, the Receptor of a Fluorescent Chemosensor for Cu2+

“…Theoretical studies of calix[4]­arenes, thiacalix[4]­arenes, and their derivatives to date have predominantly focused on the investigation of ground-state properties, such as conformations, − binding sites, and binding energy of metal complexes. − Only a few studies have been performed examining the UV spectra and excited-state properties of these molecules using TD-DFT. − Fu et al performed TD-DFT calculations to simulate the absorption and emission spectra of neutral TCA and its complex with tetranuclear cadmium­(II), in which the phenol group of thiacalix[4]­arene was deprotonated . The calculated results were in excellent agreement with the experimental data.…”