Organic molecules as well as metal complexes may exist as several geometric isomers1 which display distinct physical properties and chemical reactivities. A molecule containing two atoms (in general, two carbons) attached together by a double bond with substituents W-Z may be found as two isomeric † C.D. dedicates this review to Professor Andrée Marquet as a mark of his admiration and gratitude. * To whom correspondence should be addressed: Tel: (33) 169 08 52 25. Fax: (33) 169 08 90 71. E-mail: christophe.dugave@cea.fr. ‡ Present address: Département de Chimie, Institut de Pharmacologie, Université de Sherbrooke, 3001, 12e Avenue nord, Sherbrooke, Québec, J1H 5N4 Canada. 2475 Chem. Rev. 2003, 103, 2475−2532

Cis-trans isomerization of organic molecules and biomolecules: implications and applications.

Iniferters are initiators that induce radical polymerization that proceeds via initiation, propagation, primary radical termination, and transfer to initiator. Because bimolecular termination and other transfer reactions are negligible, these polymerizations are performed by the insertion of the monomer molecules into the iniferter bond, leading to polymers with two iniferter fragments at the chain ends. The use of well-designed iniferters would give polymers or oligomers bearing controlled end groups. If the end groups of the polymers obtained by a suitable iniferter serve further as a polymeric iniferter, these polymerizations proceed by a living radical polymerization mechanism in a homogeneous system. In these cases, the iniferters (CS bond) are considered a dormant species of the initiating and propagating radicals. In this article, I describe the history, ideas, and some characteristics of iniferters and living radical polymerization with some iniferters that contain dithiocarbamate groups as photoiniferters and several compounds as thermal iniferters. From the viewpoint of controlled polymer synthesis, iniferters can be classified into several types: thermal or photoiniferters; monomeric, polymeric, or gel iniferters; monofunctional, difunctional, trifunctional, or polyfunctional iniferters; monomer or macromonomer iniferters; and so forth. These lead to the synthesis of various monofunctional, telechelic, block, graft, star, and crosslinked polymers. The relations between this work and other recent studies are discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2121–2136, 2000

https://onlinelibrary.wiley.com/doi/epdf/10.1002/%28SICI%291099-0518%2820000615%2938%3A12%3C2121%3A%3AAID-POLA10%3E3.0.CO%3B2-X

Iniferter concept and living radical polymerization

Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications

Coordination chemistry of the larger calixarenes

Calixarenes, as nano-baskets, are considered an important group of macrocycles as the third famous host molecules after cyclodextrins and crown ethers have been subject to extensive researches in construction of many extractants, transporters, stationary phases, electrode ionophores and optical and electrochemical sensors over the past four decades. Because of the recent rapid growth in the publications of calixarene applications, this review paper has focused on different analytical applications of calixarenes in the main fields of separation, electroanalysis, spectroscopy and chemometrics. The objectives and the results of about 300 references mainly were published in recent 6 years with emphasis on the analytical applications were reviewed.

Analytical applications of calixarenes from 2005 up-to-date

The selective liquid-liquid extraction of various alkali and transition metal cations from the aqueous phase to the organic phase was carried out by using p-tert-butylcalix[4]arene (L1), p-tert-butylcalix[6]arene (L2), tetra-ethyl p-tert-butylcalix[4]arene-tetra-acetate (L3), tetra-methyl-p-tert-butyl-calix[4]arene-tetra-ketone (L4), calix[n]arenes (n=4 and 6) bearing oxime groups on the lower rim (L5, L6 ) and a polymeric calix[4]arene. It was found that compounds L5 and L6, showed selectivity towards Ag+, Hg+, Hg2+, Cu2+, and Cr33+ and the order of the extractability was Hg+>Hg2+>Ag+>Cu2+>Cr3+. The polymeric calix[4]arene (L8) was selective for Ag+, Hg+ and Hg2+, unlike its monomeric analog.

Liquid-liquid extraction of transition metal cations by calixarene-based cyclic ligands

Selective complexation of Na by polymeric calix[4]arene tetraesters

Comparative studies on the solvent extraction of transition metal cations by calixarene, phenol and ester derivatives.

Three polymeric calix[4]arenes were synthesized by reacting chloromethylated polystyrene with 25,26,27-tribenzoyloxy-28-hydroxy calix[4]arene (2a, 3a) and polyacryloyl chloride with 25,26,27,28-tetraacetoxy calix[4]arene (4a). After alkaline hydrolysis of the polymers, they were utilised for selective extraction of some transition metal cations from aqueous phase to organic phase. It was found that the polymeric calix[4]arenes were selective to extract Fe3+ from an aqueous solution which contained Cu2+, Ni2+, Co2+, and Fe3+ cations and it was observed that the polymer supported onto the lower rim calix[4]arene is a more efficient carrier of Fe3+ in the extraction process.

Synthesis of polymer-supported calix[4]arenes and selective extraction of Fe3+

Azocalixarenes, which have a conjugated chromophore azo (–N=N–) group in p-positions, are synthesized in “one-pot” procedures in satisfactory yields. Their structures in the solid and solution are elucidated by UV–vis, FT-IR, 1H and 13C NMR spectroscopic methods as well as elemental analysis techniques. Some of them are complexed with metal ions (alkali, alkaline-earth and transition metal ions) under neutral conditions. A wide variety of applications is expected by the functionalization of the side arms. The selective liquid–liquid extraction of various alkali, alkaline-earth and transition metal cations from the aqueous phase to the organic phase is carried out by using azocalixarenes. Furthermore, the synthesized azocalixarenes are utilized for selective extraction of Fe3+ cations from the aqueous phase to the organic phase. The effects of varying pH and solvent upon the absorption ability of azocalixarenes substituted with electron-donating and electron-withdrawing groups at their o-, m-, p-positions are examined. The thermal behaviours of azocalixarenes containing upper rim functionalized groups are investigated by means of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG).

Hasalettin Deligöz

Papers

Liquid-liquid extraction of transition metal cations by calixarene-based cyclic ligands

Selective complexation of Na by polymeric calix[4]arene tetraesters

Comparative studies on the solvent extraction of transition metal cations by calixarene, phenol and ester derivatives.

Synthesis of polymer-supported calix[4]arenes and selective extraction of Fe3+

Azocalixarenes: Synthesis, Characterization, Complexation, Extraction, Absorption Properties and Thermal Behaviours