Conjugated Polymetallorotaxanes: In-Situ ESR and Conductivity Investigations of Metal−Backbone Interactions
Conjugated Polymetallorotaxanes: In-Situ ESR and Conductivity Investigations of Metal−Backbone Interactions
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DOI：
10.1021/jp021827d
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发表时间：
2003-05
影响因子：
3.3
通讯作者：
B. Divisia-Blohorn;F. Genoud;C. Borel;G. Bidan;J. Kern;J. Sauvage
中科院分区：
文献类型：
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作者：
B. Divisia-Blohorn;F. Genoud;C. Borel;G. Bidan;J. Kern;J. Sauvage
本文报道了通用式聚[1,3，Mn+]的多金属紫外光膜的电化学研究，其中Mn+是铜(I)，钴（II），锌（II）或锂(I)，用于金属化和脱金属（聚[1,3,-]）形式。除Li外，含有氧化还原活性金属的多金属紫菀烷的循环伏安（CV）记录除了络合金属的电活性外，还显示出与接线聚合物中低硫乙烯单元的连续氧化/还原相关的两个氧化还原对。对于聚[1,3,Cu+]， CV研究是通过ESR光谱电化学研究结合作为电极电位函数的原位电导率测量完成的。在ESR响应中，可以区分两种不同来源的信号：来自Cu（II）顺磁性离子的宽信号（约265 G的ΔHpp）和来自聚合物主链的不成对自旋的宽信号（约21 G的ΔHpp）。这两种信号的潜在依赖性以及潜在诱导的相互作用。
Electrochemical studies of polymetallorotaxane films of a general formula poly[1,3,Mn+] where Mn+ is copper(I), cobalt(II), zinc(II), or lithium(I) are reported for both metalated and demetalated (poly[1,3,-]) forms. Cyclic voltammograms (CV) recorded for polymetallorotaxanes containing redox-active metals, with an exception of the Li one, in addition to the electroactivity of the complexing metal exhibit two redox couples associated with the consecutive oxidation/reduction of the oligothienylene units in the wiring polymer. For poly[1,3,Cu+], the CV studies are completed by ESR spectroelectrochemical investigations combined with in-situ conductivity measurements as a function of the electrode potentials. In the ESR response, two signals of different origin can be distinguished: a broad signal originating from Cu(II) paramagnetics ions (ΔHpp of ca. 265 G) and that due to unpaired spins of the polymer backbone (ΔHpp of ca. 21 G). Potential dependencies of these two signals as well as potential-induced con...