Discrete polynuclear manganese(ii) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties

Yan Suffren (1) , Niall O'Toole (2) , Andreas Hauser (1) , Erwann Jeanneau (2) , Arnaud Brioude (2) , Cedric Desroches (2)

1 Département de chimie physique [Genève]
2 LMI - Laboratoire des Multimatériaux et Interfaces

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 Mn2+ centred 4T1→6A1 transition. Its temperature and pressure dependence and quenching by molecular dioxygen are reported. The latter is attributed to energy transfer from the 4T1 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.

Domaines: Chimie de coordination

Yan Suffren, Niall O'Toole, Andreas Hauser, Erwann Jeanneau, Arnaud Brioude, et al.. Discrete polynuclear manganese(ii) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties. Dalton Transactions, 2015, 44 (17), pp.7991-8000. ⟨10.1039/c5dt00827a⟩. ⟨hal-01597128⟩