Orientation-Induced Redox Isomerism in Planar Supramolecular Systems

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• 作者：Sofiya L. Selektor ; Alexander V. Shokurov ; Vladimir V. Arslanov ; Yulia G. Gorbunova ; Kirill P. Birin ; Oleg A. Raitman ; Fabien Morote ; Touria Cohen-Bouhacina ; Christine Grauby-Heywang ; Aslan Yu. Tsivadze
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：February 27, 2014
• 年：2014
• 卷：118
• 期：8
• 页码：4250-4258
• 全文大小：444K
• 年卷期：v.118,no.8(February 27, 2014)
• ISSN：1932-7455

文摘

In this work, a previously undescribed phenomenon of orientation-induced redox isomerism in a Langmuir monolayer is revealed in the case of cerium bis-[tetra-(15-crown-5)-phthalocyaninate]-(Ce[(15C5)₄Pc]₂). It was established that intramolecular electron transfer (IET) from the electronic system of phthalocyanine to the 4f-orbital of cerium atom occurs upon spreading of a (Ce[(15C5)₄Pc]₂) chloroform solution onto the air鈥搘ater interface (3D 鈫?2D IET). This process is related to the transformation of Ce⁴⁺ cation in the solution to Ce³⁺ in the monolayer. It was also found that reversible Ce³⁺ 鈫?Ce⁴⁺ IETs occur upon compression (蟺₁ 鈫?蟺₂) and expansion (蟺₂ 鈫?蟺₁) of monolayer (2D^蟺1 鈫?2D^蟺2 IET, 蟺-surface pressure). The mechanism of genuine redox isomerism was confirmed by the results of in situ UV鈥搗is spectral measurements performed on monolayers and Langmuir鈥揃lodgett films, AFM, and XPS studies of Langmuir鈥揃lodgett films transferred at different surface pressures. The understanding of this reversible IET mechanism is especially important due to possible applications of such redox-isomeric systems in the development of nanoscale multibit information storage devices.