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Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties
Author(s) -
O'Toole Niall,
Lecourt Constance,
Suffren Yan,
Hauser Andreas,
Khrouz Lhoussain,
Jeanneau Erwann,
Brioude Arnaud,
Luneau Dominique,
Desroches Cédric
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801104
Subject(s) - chemistry , luminescence , manganese , electron paramagnetic resonance , photochemistry , quenching (fluorescence) , spectroscopy , crystallography , fluorescence , organic chemistry , physics , optoelectronics , nuclear magnetic resonance , quantum mechanics
The photophysical properties of the compound [(ThiaSO 2 )(Mn II ) 2 (DMF) 4 (H 2 O) 2 ] ( 2 ), ThiaSO 2 = p ‐ tert ‐butylsulfonylcalix[4]arene, are presented and compared to the ones of [(ThiaSO 2 ) 2 (Mn II ) 4 F]K ( 1 ). The orange luminescence of 2 is attributed, as for 1 , to the Mn II centred 4 T 1 → 6 A 1 transition and shows, for this type of complex, the weak influence of the Mn 2+ coordination and ThiaSO 2 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 4 T 1 state exciting dioxygen to its 1 Σ + g state and is responsible for the photosynthesis of the [(ThiaSO 2 )(Mn III )(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.