Suffren Yan, O'Toole Niall, Hauser Andreas, Jeanneau Erwann, Brioude Arnaud, Desroches Cédric
Département de chimie physique, Université de Genève, 30 Quai Ernest-Ansermet, 1211 Genève 4, Switzerland.
Dalton Trans. 2015 May 7;44(17):7991-8000. doi: 10.1039/c5dt00827a.
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.
介绍了新化合物[Mn4(ThiaSO2)2F][K(18-冠-6)]（其中ThiaSO2 = 对叔丁基磺酰基杯[4]芳烃）的合成、晶体结构和光物理性质，并与[Mn4(ThiaSO2)2F]K的相关性质进行了比较。强烈的橙色发光归因于以Mn(2+)为中心的(4)T1→(6)A1跃迁。报道了其温度和压力依赖性以及被分子态氧气猝灭的情况。后者归因于从激发氧气的(4)T1态到其(1)∑(+)g态的能量转移。在固态中，[Mn4(ThiaSO2)2F][K(18-冠-6)]中的猝灭比[Mn4(ThiaSO2)2F]K中的效率高得多。这归因于前者的开孔结构允许氧气快速扩散到晶格中。
