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DOI: 10.1039/A706933B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 497-504

Structural and dynamic properties of calixarene bimetallic complexes: solution versus solid-state structure of dinuclear complexes of EuIII and LuIII with substituted calix[8]arenes[hair space]†

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Jean-Claude G. Bünzli, Frédéric Ihringer, Pascal Dumy, Cédric Sager and Robin D. Rogers

Abstract

The solid state (Ln = Eu) and solution (Ln = Lu) structure of the dinuclear complexes [Ln2L(dmf[hair space])5]·xsolv, where L is the hexaanion of p-nitrocalix[8]arene (n-H8L) or p-tert-butylcalix[8]arene (b-H8L) and dmf = dimethylformamide, have been analysed and compared. The neutral [Eu2(n-H2L)(dmf[hair space])5] species displays C2 symmetry with the axis perpendicular to the Eu–Eu internuclear axis. The europium(III) ions are separated by 3.810(1) Å and are surrounded by eight O atoms, with six Eu–O distances in the range 2.2–2.4 Å (two phenoxides, two µ-phenoxides and two dmf[hair space]) while the remaining Eu–O bond lengths are much longer (2.7–2.9 Å, one phenol and one µ-dmf[hair space]). The geometry of the dinuclear assembly is comparable to that observed for [Eu2(b-H2L)(dmf[hair space])5]·4dmf, both ligands adopting a two-bladed propeller conformation. The solution structure of [Lu2L(dmf[hair space])5], L = b-H2L6– and n-H2L6–, has been investigated by 1H NMR spectroscopy in [2H7]dmf. The dinuclear complexes retain a two-fold symmetry element and the ligand conformation is identical for both edifices and very close to the solid-state conformation. An intramolecular racemisation process has been evidenced and characterised at 294 K: k = 7.0 ± 0.7 s–1, ΔG‡ = 67.1 ± 0.4 kJ mol–1 (b-H8L) and k = 1.1 ± 0.1 s–1, ΔG‡ = 71.6 ± 0.4 kJ mol–1 (n-H8L).

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