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Pyridinium based ionic liquids form complexes with meso-octamethylcalix[4]pyrrole with both the anion and cation binding to the tetrapyrrole macrocycle.

Metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles have been structurally characterised for the first time, complementing the significant amount of work that has been reported for the analogous pyridine ligands. N,N′-Bis(3,5-dinitrophenyl)-3,4-diphenyl-1H-pyrrole-2,5-dicarboxamide forms octahedral bis(tridentate) complexes with cobalt(III) and nickel(II), where the ligands are bound to the metal centres through deprotonated pyrrole and amide N atoms. N,N′-Dibutyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide and N,N′-diphenyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide also form bis(tridentate) cobalt complexes but are only deprotonated at the pyrrole N atom, the remainder of the coordination sphere comprising the thioamide S atoms. The dibutyl derivative was isolated as a Co(II) complex, whereas the diphenyl system deposited a Co(III) complex. In contrast, N,N′-dibutyl-3,4-dichloro-1H-pyrrole-2,5-dicarboxamide was found to act as a bidentate ligand, in an octahedral cobalt(II) complex comprising of two bidentate pyrrole ligands, and two aqua ligands. Synthesis of N,N-bis(pyridin-2-ylmethyl)-3,4-diphenyl-1H-pyrrole-2,5-carboxamide gave a pyrrole ligand with increased denticity. Reaction with cobalt(II) chloride resulted in the isolation of a dinuclear helicate complex. The ligand was found to have undergone addition of a methoxy group to one of the linking methylene carbons, presumably as a result of the oxidative addition of solvent methanol.

International audience; Proton NMR titrations have been performed with meso-octacalix[4]pyrrole and a variety of organic chloride and bromide salts in dichloromethane-d2. The results show apparently increasing chloride stability constants within each set of anion salts (tetrabutylammonium < imidazolium < pyridinium). Addition of 1-ethyl-3-methylimidaolium (EMIM) nitrate to dichloromethane-d2 solutions of calix[4]pyrrole caused significantly larger downfield shifts of the pyrrole NH protons of calix[4]pyrrole than addition of equimolar quantities of tetrabutylammonium nitrate. The first crystal structure of a nitrate complex of a calix[4]pyrrole is also presented.

This review article provides a broad overview to the area of anion coordination by synthetic organic receptors and includes examples of different functional groups used to bind anions. The first section examines neutral anion receptors containing amide-, sulfonamide-, urea- and thiourea-based receptors. Then aromatics such as pyrrole, carbazole and indole are discussed before concluding the discussion of neutral systems with examples of hydroxy OH donors. A brief overview of charged systems is also provided.

The first crystal structures of anion complexes of N-confused calix[4]pyrrole are presented showing chloride binding to the three ‘unconfused’ pyrrole NH groups and imidazolium inclusion in the calixpyrrole cup.