The tris-p-(tert-butyl)calix[4]arene has been synthesized by a reproducible selective esterification-dealkylation-saponification process.

The octopode 1, prepared by alkylation of 2, 8, 14, 20-tetra(methyl)calix[4]resorcinarene with 6-bromomethyl-6′-methyl-2,2′-bipyridine, was reacted with anhydrous CoCl2, affording the corresponding octo(dichlorocobaltII) complex 2.

The synthesis of [Cu(6,6'-dimethyl-2,2'-bipyrazine)(2)][BF4] (4), [Cu(2,2'-dimethyl-6,6'-diphenyl-4,4'-bipyrimidine)(2)]-[PF6] (3), and catena-poly-[(2,2'-dimethyl-4,4'-bipyrimidine-N,N',N')bis(acetonitrile)dicopper(I)] (5) was realized from the corresponding free heterocyclic ligands. X-ray structures of the two last products were determined, and their structural data are as follows. 3: chemical formula (CuN8C44H36PF6; lattice constants with esd's (a-c, Angstrom; alpha-gamma, deg) 12.089(1), 16.229(7), 21.196(3), 90, 98.46(1), 90; crystal system monoclinic; space group P2(1)/n; Z = 4. 4: chemical formula CuN8C20H20BF4. 5: chemical formula CuN5C12H13PF6; lattice constants with esd's (a-c, A; alpha-gamma, deg) 12.900(3), 8.773(3), 14.702(4); 90, 101.99(2), 90; crystal system monoclinic; space group P2(1)/n; Z = 4. The proton NMR and crystallographic results of the unsubstituted 4,4'-bipyrimidine show that both inner and outer nitrogens are involved in the coordination metal center process, giving a structure of an infinite-chain copper(I) polymer.

The hetero-armed p-(tert-butyl)calix[4]arene 1 was synthesized by a stepwise procedure. This ligand presented a very strong complexing behavior towards Cu-I, giving the chiral complex 2 and parent species when reacted with Cu-II salts. High-resolution NMR techniques were employed for the characterization of 2, demonstrating notably exchange processes between its two enantiomeric forms. The racemic nature of 2 was confirmed by X-ray crystal-structure analysis.

The synthesis of 2,2'-dimethyl-4,4'-bipyrimidine (bpm) and 6,6'-dimethyl-2,2'-bipyrazine (bpz) is described. In these compounds the s-trans molecular conformation has been observed and could be interpreted in terms of weak C-H...N interactions. The crystal stacking in the two compounds is formed by parallel molecular planes which are 3.46 angstrom apart. A semi-empirical calculation shows that, irrespective of the medium, the molecules conserve this preferential conformation.

The bipyridyl-armed tetra-p-(tert-butyl)calix[4]arenes 1-5 were synthesized from tetra-p-(tert-butyl)calix[4]arene A and 6-(bromomethyl)-6'-methyl 52-bipyridine (B) by direct base-strength-driven regioselective O-alkylation or by stepwise procedures. Preliminary complexation studies of the ligands 1-3 with Cu-I affording the complexes 6-8 are described.

Recently, a large number of biheterocycles have been synthesized in order to build macrobicyclic cryptates. To pursue investigations in this field, we prepared new symmetric and unsymmetric functionalized bipyridines and we describe here two synthetic strategies leading to new tetrasubstituted 3 to 15 and trisubstituted 17 to 29 bipyridines. Modification at the alpha,alpha'-methyl groups and introduction of functionalities in the 4,4'-positions have been performed after N-O activation of the starting 6,6'-dimethyl-2,2'-bipyridine unit. In the case of cyano and hydroxymethyl groups, alkylation of the N-O function followed by a nucleophilic attack with the CN anion or an hydroxymethyl radical allowed us to obtain the dissymmetric species. To understand observed differencies between cyanation and hydroxymethylation processes, the unstable and hygroscopic N-methoxybipyridinium salt 30 has been isolated and characterized by nmr. Dibromomethyl compounds 8, 15, 29 were finally obtained in good to moderate yields by the Boekelheide rearrangement followed by a pseudohalogen exchange.

As a consequence of our recent success in isolating and characterizing the first crystalline cryptatium species, the redox properties of a series of cryptates have been analyzed in DMF using cyclic voltammetry. A total of eight cryptates, derived from six cryptands, were studied (see structures in the text). These were the Na+, Ca2+, and La3+ cryptates of tris(bipyridyl) (1-Na+, 1-Ca2+, 1-La3+) and the Na+ complexes of the other five ligands, 2-6. Except for 6-Na+, which exhibited irreversible behavior, and for 2-Na+, which, as expected, had only one redox couple, all of the cryptates showed at least three quasi-reversible redox couples. For 1-La3+ a total of six cathodic waves were observed. A pronounced effect was observed for the reduction potentials when the central metal cation of the cryptate was changed. Thus for 1-Na+ the first reduction potential occurs at -2.40 V (vs ferrocene/ferrocenium, Fc/Fc+), while the corresponding value for I-La3+ is -1.76 V. On the other hand, for all of the Na+ cryptates, the redox potential of each of the individual substituent groups (bipyridyl, bithiazole, dimethylbipyrimidine) was approximately independent of the other substituents present in the molecule, although the reduction state of the complex affected these potentials. For example, the reduction potential for the bithiazole group was the same for the sodium complexes of 2 and 3 and almost the same for the first reduction of 4-Na+. Similarly, the reduction of the two bipyridyls of 3 and 5 occurred at the same potentials as those observed for the second and third reductions of I-Na+. All of the reported redox processes correspond to ligand-centered orbitals, not to those of the metals, a result consistent with the spatially-isolated orbital theory which is accepted for bipyridyl complexes of Ru2+.

The sodium cryptates of the macrobicyclic ligands 1-6 have been synthesized by direct macrobicyclisation or by stepwise procedures, They incorporate 2,2-bithiazole, 2,2-biimidazole, 2,2'-bipyrimidine as well as 2,2'-bipyridine units. Treatment of the sodium complexes with europium(III) chloride gave the corresponding Eu(III) cryptates. The structural and spectral properties of these compounds are described. The Eu(III) complexes present characteristic H-1-NMR chemical-shift features. Their luminescence properties are described.

Bulletin des Sociétés Chimiques BelgesVolume 100, Issue 9 p. 673-676 Article Tempo, a Superoxide Dismutase Mimic C. Bonne, C. Bonne Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorE. Latour, E. Latour Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorG. Modat, G. Modat Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorA. Muller, A. Muller Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorO. Palluy, O. Palluy Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorJ. B. Regnouf De Vains, J. B. Regnouf De Vains Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorG. Tissie, G. Tissie Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorS. Veriac, S. Veriac Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this author C. Bonne, C. Bonne Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorE. Latour, E. Latour Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorG. Modat, G. Modat Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorA. Muller, A. Muller Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorO. Palluy, O. Palluy Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this authorJ. B. Regnouf De Vains, J. B. Regnouf De Vains Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorG. Tissie, G. Tissie Centre de Recherche Ophtalmologique Chauvin, Montpellier, FranceSearch for more papers by this authorS. Veriac, S. Veriac Laboratoire de Physiologie Cellulaire, Université Montpellier I, FranceSearch for more papers by this author First published: 1991 https://doi.org/10.1002/bscb.19911000906Citations: 3AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume100, Issue91991Pages 673-676 RelatedInformation

The sodium cryptates of several novel macrobicycles containing 2,2′-bithiazole, 2,2′-bisimidazole and 2,2′-bipyrimidine subunits have been synthesized by a macrobicyclisation procedure; some of their properties are described.