Conjugated polyelectrolyte (CPE) poly[3-[6-(N-methylimidazolium)hexyl]-2,5-thiophene] complexed with aqueous sodium dodecylsulfate amphiphile: synthesis, solution structure and “surfactochromic” properties
Conjugated polyelectrolyte (CPE) poly[3-[6-(N-methylimidazolium)hexyl]-2,5-thiophene] complexed with aqueous sodium dodecylsulfate amphiphile: synthesis, solution structure and “surfactochromic” properties
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DOI：
10.1039/c1sm05492a
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发表时间：
2011-07
期刊：
影响因子：
3.4
通讯作者：
M. Knaapila;R. C. Evans;A. Gutacker;V. Garamus;N. Székely;U. Scherf;H. Burrows
中科院分区：
文献类型：
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作者：
M. Knaapila;R. C. Evans;A. Gutacker;V. Garamus;N. Székely;U. Scherf;H. Burrows
我们报告了聚[3-[6-（N-甲基咪唑）己基]-2，5-噻吩]溴（P3 ImiHT）与十二烷基硫酸钠（SDS）复合时的合成、溶液结构和光物理性质。P3 ImiHT的合成使用由McCullough开发的Grignard复分解（GRIM）型路线，然后用N-甲基咪唑季铵化聚[3-（6-溴己基）噻吩]的溴己基侧基。将P3 ImiHT与SDS或氘代SDS混合，在D2 O中形成P3 ImiHT（SDS）x络合物，其中x是表面活性剂与SDS重复单元的摩尔比，并使用小角中子散射（SANS）和光学光谱进行研究。与相关的聚[3-（6-三甲基铵己基）噻吩]溴化物（P3 TMAHT）相比，在P3 ImiHT与SDS的相互作用后观察到行为的显著差异。在室温下，P3 ImiHT形成具有静电排斥的带电聚集体，其通过SDS添加而消除。当x ≤ 1时，P3 ImiHT和SDS分子混合并形成椭圆形（x = 1/5）或片状（x = 1/2-1）P3 ImiHT（SDS）x聚集体。在标称电荷补偿点（x = 1）周围未观察到可见沉淀。当x > 1时，P3 ImiHT（SDS）x聚集体与SDS富集胶束共存，后者由粗棒状（x = 3/2）转变为不带电（x = 2）和带电椭圆形（x = 5）胶束。这种转变是由减少自由离子分数。当x = 5时，P3 ImiHT（SDS）x形成周期为270 A的层状相.结构转变伴随着从422 nm（x = 0）到459 nm（x = 1）的初始红移，随后是UV/维斯吸收最大值的反向蓝移到400 nm（x = 5）。光激发光谱遵循这一趋势，但红移约50 nm，从而表明光激发后的态密度内的能量转移。当x从0增加到5时，光致发光最大值从643 nm逐渐蓝移到597 nm，表明聚合物-聚合物相互作用减少。
We report on the synthesis, solution structure and photophysical properties of poly[3-[6-(N-methylimidazolium)hexyl]-2,5-thiophene] bromide (P3ImiHT) when complexed with sodium dodecylsulfate (SDS). Synthesis of P3ImiHT used a Grignard metathesis (GRIM)-type route developed by McCullough, followed by quaternisation of the bromohexyl side groups of poly[3-(6-bromohexyl)thiophene] with N-methylimidazole. P3ImiHT was mixed with either SDS or deuterated SDS to form the P3ImiHT(SDS)x complex, where x is the molar ratio of surfactant to polyelectrolyte repeat unit, in D2O and studied using small-angle neutron scattering (SANS) and optical spectroscopy. Marked differences in behaviour are observed upon interaction of P3ImiHT with SDS compared with the related poly[3-(6-trimethylammoniumhexyl)thiophene] bromide (P3TMAHT). At room temperature, P3ImiHT forms charged aggregates with electrostatic repulsion which are eliminated by the SDS addition. For x ≤ 1 P3ImiHT and SDS are molecularly mixed and form ellipsoidal (x = 1/5) or sheet-like (x = 1/2–1) P3ImiHT(SDS)x aggregates. No visible precipitation is observed around the nominal charge compensation point (x = 1). For x > 1, P3ImiHT(SDS)x aggregates coexist with SDS rich micelles which turn from thick rod-like (x = 3/2) to non-charged (x = 2) and charged ellipsoidal micelles (x = 5). This transition is driven by decreasing free ion fraction. For x = 5, P3ImiHT(SDS)x forms a lamellar phase with a periodicity of ∼270 A. The structural transitions are accompanied by an initial red-shift from 422 nm (x = 0) to 459 nm (x = 1), followed by a reverse blue-shift to 400 nm (x = 5) of the UV/vis absorption maxima. The photoexcitation spectra follow this trend but are ∼50 nm red-shifted, thus indicating energy transfer within the density of states after photoexcitation. The photoluminescence maximum is gradually blue-shifted from 643 nm to 597 nm on increasing x from 0 to 5, indicating a decrease in polymer–polymer interactions.