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DOI: 10.1039/A706152H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 505-510

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties[hair space]†

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Loïc J. Charbonnière, Christian Balsiger, Kurt J. Schenk and Jean-Claude G. Bünzli

Abstract

Spectrophotometric pKa determination for p-tert-butylcalix[5]arene (H5L) in acetonitrile (pKa1 = 11.5 ± 0.7, pKa2 = 15.4 ± 1.0 at 298 K) evidenced both intra- and inter-molecular stabilisation of the deprotonated forms. Dimeric complexes [Ln2(H2L)2(dmso)4] (Ln = EuIII, GdIII, or TbIII; dmso = dimethyl sulfoxide) were isolated from tetrahydrofuran (thf[hair space]) in the presence of NaH as base. A single-crystal analysis of [Eu2(H2L)2(dmso)4]· 10thf showed the deformation of the cone conformation of the calixarene upon complexation and co-ordination of dmso molecules by inclusion through the hydrophobic cavity of the ligand. A photophysical investigation revealed a total quenching of the metal luminescence by a ligand-to-metal charge-transfer state in the case of EuIII while luminescence of TbIII is sensitised (quantum yield in thf: 5.1%). The temperature-dependent lifetime of TbIII is analysed in terms of a potential metal-to-ligand back-transfer process.

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