The synthesis of a new amphiphilic 5,5′,6,6′-tetrachlorobenzimidacarbocyanine dye derivative with −(CH₂)₂–(CF₂)₅–CF₃ chains attached to the nitrogen atoms in the 1,1′-position, CF8O3, is reported. Depending on the dye concentration and the addition of MeOH, CF8O3 forms J- and H-aggregates in aqueous solutions. The aggregation behavior was investigated using steady-state absorption, linear dichroism, and fluorescence spectroscopy, as well as by cryogenic transmission electron microscopy (cryo-TEM). The J-band of the MeOH-free solution is monomer-like, rather broad, and less red-shifted with respect to the monomer absorption, indicating weak excitonic coupling and disorder effects. Cryo-TEM reveals a diversity of supramolecular structures, wherein linear and branched cylindrical micelles dominate. It is concluded that the high stiffness of fluoroalkyl chains does not allow the chains to splay and completely fill up the hydrophobic gap between opposing chromophores. This destabilizes the bilayers and favors the micellar structure motifs instead. The aggregates appearing at 30% MeOH show a split absorption spectrum consisting of a broad blue-shifted H-band and an accompanying sharp red-shifted J-band with perpendicular polarizations. These HJ-type aggregates are also composed of micellar fibers, but these bundle into rope-like strands. For 10% MeOH, a narrow bilayered tube is the dominating morphology. The observed MeOH dependence of aggregation reveals a clear cosolvent effect.

中文翻译：

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两亲碳菁的聚集：氟化有利于圆柱形胶束而不是双层管

具有-(CH ₂ ) ₂ –(CF ₂ ) ₅ –CF ₃的新型两亲性 5,5',6,6'-四氯苯并亚胺碳菁染料衍生物的合成据报道，连接到 1,1' 位氮原子的 CF8O3 链。根据染料浓度和 MeOH 的添加，CF8O3 在水溶液中形成 J-和 H-聚集体。使用稳态吸收、线性二色性和荧光光谱以及低温透射电子显微镜 (cryo-TEM) 研究聚集行为。不含甲醇的溶液的 J 带类似于单体，相当宽，并且相对于单体吸收的红移较少，表明弱激子耦合和无序效应。Cryo-TEM 揭示了多种超分子结构，其中线性和分支的圆柱形胶束占主导地位。得出的结论是，氟烷基链的高刚度不允许链张开并完全填满相对生色团之间的疏水间隙。这使双层不稳定并有利于胶束结构图案。出现在 30% MeOH 处的聚集体显示出由宽蓝移 H 带和伴随垂直偏振的急剧红移 J 带组成的分裂吸收光谱。这些 HJ 型聚集体也由胶束纤维组成，但这些纤维束成绳状。对于 10% MeOH，狭窄的双层管是主要形态。观察到的聚集对 MeOH 的依赖性揭示了明显的共溶剂效应。出现在 30% MeOH 处的聚集体显示出由宽蓝移 H 带和伴随垂直偏振的急剧红移 J 带组成的分裂吸收光谱。这些 HJ 型聚集体也由胶束纤维组成，但这些纤维束成绳状。对于 10% MeOH，狭窄的双层管是主要形态。观察到的聚集对 MeOH 的依赖性揭示了明显的共溶剂效应。出现在 30% MeOH 处的聚集体显示出由宽蓝移 H 带和伴随垂直偏振的急剧红移 J 带组成的分裂吸收光谱。这些 HJ 型聚集体也由胶束纤维组成，但这些纤维束成绳状。对于 10% MeOH，狭窄的双层管是主要形态。观察到的聚集对 MeOH 的依赖性揭示了明显的共溶剂效应。