Dynamics of charge carriers on poly[bis(p-alkylphenyl)silane]s by electron beam pulse radiolysis
Dynamics of charge carriers on poly[bis(p-alkylphenyl)silane]s by electron beam pulse radiolysis
复制标题
电子束脉冲辐射分解聚[双(对烷基苯基)硅烷]载流子动力学
DOI：
10.1021/jp025617c
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发表时间：
2002
影响因子：
3.3
通讯作者：
M. Fujiki
中科院分区：
文献类型：
--
作者：
S. Seki;Yoshinori Matsui;Y. Yoshida;S. Tagawa;J. Koe;M. Fujiki
用电子束脉冲辐解方法研究了聚双对烷基苯基硅烷离子自由基沿着聚合物骨架的电子离域程度。Si链上负电荷的离域程度强烈依赖于苯环上烷基（正丁基和叔丁基）的取代位置，尽管观察到空穴的影响相对较小。振子强度和离域度（ndel）之间的经验关系给出了聚[双（对-正丁基苯基）硅烷]上过量电子的ndel值为1036 Si单元，而聚[双（对-叔丁基苯基）硅烷]的ndel值为14，这与聚（甲基苯基硅烷）的ndel值相似。聚双（对烷基苯基）硅烷阳离子自由基的振子强度（f·+ > 0.65）比聚甲基苯基硅烷阳离子自由基的振子强度（f·+ = 0.35）高1.2倍。正电荷使聚双（对烷基苯基）硅烷的离域程度高于聚甲基苯基硅烷。
The degree of electron delocalization along polymer skeletons was discussed for ion radicals of poly[bis(p-alkylphenyl)silane]s by electron beam pulse radiolysis. The degree of delocalization of negative charges on the Si chains strongly depended on the substitution position of the alkyl groups (n- and tert-butyl) on the phenyl rings, though relatively small effects were observed for holes. The empirical relationship between oscillator strength and the degree of delocalization (ndel) gave the value of ndel as ∼36 Si units for excess electrons on poly[bis(p-n-butylphenyl)silane] in contrast to the value of ndel = 14 for poly[bis(p-t-butylphenyl)silane], which was similar to that for poly(methylphenylsilane). The oscillator strength of the cation radicals of poly[bis(p-alkylphenyl)silane]s (f•+ > 0.65) was ∼2 times higher than that of poly(methylphenylsilane) (f•+ = 0.35). Positive charges gave a higher degree of delocalization in poly[bis(p-alkylphenyl)silane]s in comparison with that in poly(methylphenyls...