Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties

Niall O'Toole; Constance Lecourt; Yan Suffren; Andreas Hauser; Lhoussain Khrouz; Erwann Jeanneau; Arnaud Brioude; Dominique Luneau; Cédric Desroches

Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties

Niall O'Toole ¹ Constance Lecourt ¹ Yan Suffren ^{2, 3} Andreas Hauser ³ Lhoussain Khrouz ⁴ Erwann Jeanneau ¹ Arnaud Brioude ¹ Dominique Luneau ¹ Cédric Desroches ¹

1 LMI - Laboratoire des Multimatériaux et Interfaces

2 ISCR - Institut des Sciences Chimiques de Rennes

3 UNIGE - Université de Genève

4 LC - Laboratoire de Chimie - UMR5182

Abstract : The photophysical properties of the compound [(ThiaSO2)(MnII)2(DMF)4(H2O)2] (2), ThiaSO2 = p‐tert‐butylsulfonylcalix[4]arene, are presented and compared to the ones of [(ThiaSO2)2(MnII)4F]K (1). The orange luminescence of 2 is attributed, as for 1, to the MnII centred 4T1→6A1 transition and shows, for this type of complex, the weak influence of the Mn2+ coordination and ThiaSO2 conformation on this luminescence, the temperature and pressure dependence and quenching by molecular dioxygen of which are reported for 2. The latter is attributed to energy transfer from the 4T1 state exciting dioxygen to its 1Σ+g state and is responsible for the photosynthesis of the [(ThiaSO2)(MnIII)(DMF)2]Na (3) complex in DMF solution from 1 or 2. This reaction was studied by UV/Visible and EPR spectroscopy. The molecular structure and EPR spectroscopy of 3 are also presented.

Keywords : Photooxidation Anganese Luminescence Thiacalixarene

Document type :

Journal articles

Domain :

Chemical Sciences / Coordination chemistry

Chemical Sciences / Inorganic chemistry

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Submitted on : Wednesday, December 5, 2018 - 10:59:33 AM
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Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties

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