Photooxidation and photoconductivity of polyferrocenylsilane thin films
Photooxidation and photoconductivity of polyferrocenylsilane thin films
复制标题
DOI：
10.1002/macp.200390061
复制
发表时间：
2003-05-07
影响因子：
2.5
通讯作者：
Sargent, EH
中科院分区：
文献类型：
--
作者：
Cyr, PW;Tzolov, M;Sargent, EH
聚二茂铁甲基苯基硅烷（[Fe（eta（5）-C_5H_4）（2）SiMePh]（n））薄膜在氯仿溶液中的紫外光照射导致聚合物主链中二茂铁中心的光氧化。聚合物氧化的程度可以控制在ca. 0-5%的辐射暴露的持续时间和氯仿的浓度。光氧化的聚二茂铁基硅烷材料是导电的，相对于未氧化的材料具有大于三个数量级的增加的电导率。此外，已发现光氧化的聚合物是光电导的。光氧化过程可以通过使用肼或十甲基二茂铁的化学还原来逆转，导致中性聚合物的再生。然而，在光氧化/还原过程中检测到大量的分子量下降，推测是由于由阴离子或自由基氯化光产物诱导的链裂解反应。发现聚合物中二茂铁部分的环戊二烯基环的甲基化导致显著更稳定的材料。
Irradiation of thin films of poly(ferrocenylmethylphenylsilane) ([Fe(eta(5)-C5H4)(2)SiMePh](n)) cast from cholorform solution with UV light leads to photooxidation of ferrocene centers in the polymer main chain. The extent of the polymer oxidation can be controlled in the range ca. 0-5% by the duration of the irradiation exposure and by the concentration of chloroform. The photooxidized polyferrocenylsilane material is conductive, with an increased conductivity of greater than three orders of magnitude relative to the unoxidized material. In addition, the photooxidized polymers have been found to be photoconductive. The photooxidation process can be reversed by means of chemical reduction using hydrazine or decamethylferrocene, leading to the regeneration of the neutral polymers. However, substantial molecular weight decline was detected during the photooxidation/reduction process, presumably as a result of chain cleavage reactions induced by the anionic or radical chlorinated photoproducts. Methylation of the cylcopentadienyl rings of the ferrocene moiety in the polymer was found to lead to materials which are significantly more stable.