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Redox-Modulations of Photophysical and Single-molecule Magnet Properties in Ytterbium Complexes Involving Extended-TTF Triads
Molecules ( IF 4.2 ) Pub Date : 2020-01-23 , DOI: 10.3390/molecules25030492
Bertrand Lefeuvre 1 , Jessica Flores Gonzalez 1 , Frédéric Gendron 1 , Vincent Dorcet 1 , François Riobé 2 , Vladimir Cherkasov 3 , Olivier Maury 2 , Boris Le Guennic 1 , Olivier Cador 1 , Viacheslav Kuropatov 3 , Fabrice Pointillart 1
Affiliation  

The reaction between the 2,2’-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate triad (H2SQ) and the metallo-precursor [Yb(hfac)3]⋅2H2O led to the formation of a dinuclear coordination complex of formula [Yb2(hfac)6(H2SQ)]⋅0.5CH2Cl2 (H2SQ-Yb). After chemical oxidation of H2SQ in 2,2’-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q), the latter triad reacted with the [Yb(hfac)3]⋅2H2O precursor to give the dinuclear complex of formula [Yb2(hfac)6(Q)] (Q-Yb). Both dinuclear compounds have been characterized by X-ray diffraction, DFT optimized structure and electronic absorption spectra. They behaved as field-induced Single-Molecule Magnets (SMMs) nevertheless the chemical oxidation of the semiquinone to quinone moieties accelerated by a factor of five the relaxation time of the magnetization of Q-Yb compared to the one for H2SQ-Yb. The H2SQ triad efficiently sensitized the YbIII luminescence while the chemical oxidation of H2SQ into Q induced strong modification of the absorption properties and thus a quenching of the YbIII luminescence for Q-Yb. In other words, both magnetic modulation and luminescence quenching are reached by the oxidation of the protonated semiquinone into quinone.

中文翻译:

涉及扩展-TTF 三元组的镱配合物中光物理和单分子磁体性质的氧化还原调制

它们表现为场诱导单分子磁铁 (SMM),但与 H2SQ-Yb 相比,半醌到醌部分的化学氧化加速了 Q-Yb 磁化弛豫时间的五倍。H2SQ 三元组有效地敏化 YbIII 发光,而 H2SQ 化学氧化成 Q 诱导吸收特性的强烈改变,从而淬灭 Q-Yb 的 YbIII 发光。换句话说,通过将质子化的半醌氧化成醌来实现磁性调制和发光猝灭。H2SQ 三元组有效地敏化 YbIII 发光,而 H2SQ 化学氧化成 Q 诱导吸收特性的强烈改变,从而淬灭 Q-Yb 的 YbIII 发光。换句话说,通过将质子化的半醌氧化成醌来实现磁性调制和发光猝灭。H2SQ 三元组有效地敏化 YbIII 发光,而 H2SQ 化学氧化成 Q 诱导吸收特性的强烈改变,从而淬灭 Q-Yb 的 YbIII 发光。换句话说,通过将质子化的半醌氧化成醌来实现磁性调制和发光猝灭。
更新日期:2020-01-23
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