期刊
INORGANICS
卷 6, 期 3, 页码 -出版社
MDPI
DOI: 10.3390/inorganics6030073
关键词
ruthenium; metallamacrocycle; electrochemistry; spectroelectrochemistry
资金
- University of Konstanz
- state of Baden-Wurttemberg
We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the case of the thioacetyl-appended complex 4, by X-ray crystallography. Cyclic and square wave voltammetry establish that the macrocycles can be oxidized in four consecutive redox steps that come as two pairs of two closely spaced one-electron waves. Spectroscopic changes observed during IR and UV/Vis/NIR spectroelectrochemical experiments (NIR = near infrared) show that the isophthalate linkers insulate the electroactive divinylphenylene diruthenium moieties against each other. The macrocycles exhibit nevertheless pronounced polyelectrochromism with highly intense absorptions in the Vis (2+/4+ states) and the NIR (2+ states) with extinction coefficients of up to >100,000 M(-1)cm(-1). The strong absorptivity enhancement with respect to the individual divinylphenylene diruthenium building blocks is attributed to conformational restrictions imposed by the macrocycle backbone. Moreover, the di- and tetracations of these macrocycles are paramagnetic as revealed by EPR spectroscopy.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据