An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities†,Organic & Biomolecular Chemistry

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An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities†
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2018-03-21 00:00:00 , DOI: 10.1039/c8ob00415c
Hendrik V. Schröder _{1,

2,

3,

4} , Felix Witte _{1,

2,

3,

4} , Marius Gaedke _{1,

2,

3,

4} , Sebastian Sobottka _{1,

2,

3,

4} , Lisa Suntrup _{1,

2,

3,

4} , Henrik Hupatz _{1,

2,

3,

4} , Arto Valkonen _{5,

6,

7,

8} , Beate Paulus _{1,

2,

3,

4} , Kari Rissanen _{5,

6,

7,

8} , Biprajit Sarkar _{1,

2,

3,

4} , Christoph A. Schalley _{1,

2,

3,

4}

Affiliation

Molecular recognition of stable organic radicals is a relatively novel, but important structural binding motif in supramolecular chemistry. Here, we report on a redox-switchable veratrole-fused tetrathiafulvalene derivative VTTF which is ideally suited for this purpose and for the incorporation into stimuli-responsive systems. As revealed by electrochemistry, UV/Vis measurements, X-ray analysis, and electrocrystallisation, VTTF can be reversibly oxidised to the corresponding radical-cation or dication which shows optoelectronic and structural propterties similar to tetrathiafulvalene and tetrakis(methylthio)tetrathiafulvalene. However, theoretical calculations, variable temperature EPR, and NIR spectroscopy indicate that the dispersion-driven binding in the mixed-valence dimer (VTTF₂)˙⁺ (K_MV = 69 M⁻¹ in CH₂Cl₂) and the radical-cation dimer (VTTF˙⁺)₂ (K_RC = 38 M⁻¹ in CH₃CN) is significantly enhanced by the additional veratrole π-surface in comparison to pristine tetrathiafulvalene.

中文翻译：

芳基稠合的氧化还原活性四硫富瓦烯，具有增强的混合价和自由基阳离子二聚体稳定性†

在超分子化学中，稳定有机自由基的分子识别是一个相对新颖但重要的结构结合基序。在这里，我们报道了一种氧化还原可转换的藜芦基融合的四硫富瓦烯衍生物VTTF，其非常适合于此目的，并且可以纳入刺激反应系统中。如通过电化学，UV / Vis测量，X射线分析和电结晶所揭示的，VTTF可以可逆地氧化为相应的自由基阳离子或阳离子，其显示出与四硫富瓦烯和四（甲硫基）四硫富瓦烯相似的光电子和结构性质。然而，理论计算，可变温度EPR和NIR光谱表明，在混合价二聚体中分散体驱动的结合（VTTF ₂）˙ ⁺（ķ _MV = 69男^-1在CH ₂氯₂）和自由基阳离子二聚体（VTTF ˙ ⁺）₂（ķ _RC = 38男^-1在CH ₃ CN）由附加显著增强与原始的四硫富瓦烯相比，其表面为π-表面。

更新日期：2018-03-21

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