title: Discrete polynuclear manganese(ii) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties.
abstract: The synthesis, crystal structure and photophysical properties of the new compound [Mn4(ThiaSO2)2F][K(18-crown-6)], ThiaSO2 = p-tert-butylsulphonylcalix[4]arene, are presented and compared to the ones of [Mn4(ThiaSO2)2F]K. The strong orange luminescence is attributed to the Mn(2+) centred (4)T1→(6)A1 transition. Its temperature and pressure dependence and quenching by molecular dioxygen are reported. The latter is attributed to energy transfer from the (4)T1 state exciting dioxygen to its (1)∑(+)g state. In the solid state, the quenching is much more efficient in [Mn4(ThiaSO2)2F][K(18-crown-6)] than in [Mn4(ThiaSO2)2F]K. This is attributed to the open pore structure of the former allowing fast diffusion of dioxygen into the crystal lattice.
authors.affiliation: Département de chimie physique, Université de Genève, 30 Quai Ernest-Ansermet, 1211 Genève 4, Switzerland. Yan.Suffren@unige.ch.
authors.forename: Yan
authors.initials: Y
authors.lastname: Suffren
authors.forename: Niall
authors.initials: N
authors.lastname: O'Toole
authors.forename: Andreas
authors.initials: A
authors.lastname: Hauser
authors.forename: Erwann
authors.initials: E
authors.lastname: Jeanneau
authors.forename: Arnaud
authors.initials: A
authors.lastname: Brioude
authors.forename: Cédric
authors.initials: C
authors.lastname: Desroches