Effects of chiral alkyl side chains in poly(9,9-dialkyl-fluorene-2,7-vinylene)s [PFVs, (S)-3-methylpentyl (3mpe), (S)-4-methylhexyl (4mhex), (S)-5-methylheptyl (5mhep), (S)-6-methyloctyl (6moct), and (S)-3,7-dimethyloctyl (dmo)] toward aggregation-induced circular dichroism (AICD) and circularly polarized luminescence (AICPL) and CD/CPL spectra in solution and in thin film have been explored. The (all-trans) PFV samples with similar conjugation repeat units containing well-defined (vinyl) end groups were prepared by acyclic diene metathesis polymerization using Ru catalyst. The PFV aggregates, prepared in situ in a mixed solution of CHCl₃/MeOH, showed clear CD signals ascribed to AICD, whereas these samples showed CD-silent in the CHCl₃ solution. The absolute magnitude (g_CD value) was affected by the chiral side chains (without obey the even–odd rule) and increased in the order 3mpe, 5mhep < 4mhex < dmo < 6mcot. Both the 6-moct and dmo aggregates showed clear CPL signals ascribed to AICPL, whereas signals of the others were not obvious. The λ_max values in the UV–vis spectra red-shifted depending upon kind of alkyl side chains due to formation of J-type aggregates. These results suggest that the optically active aggregates adopt certain helical supramolecular ordered structures induced by an interpolymer interaction through chain entanglement. The g_CD values in the drop casted thin film (prepared from the CHCl₃ solution) were lower than those in the aggregates, and the value increased in the order 5mhep, dmo < 4mhex, 6mcot < 3mpe. The λ_max values in their UV–vis spectra red-shifted but were not affected by the side chain. These results suggest that supramolecular structures formed by aggregate and film are different, and the formation in film could be induced by an interpolymer π-stacking. In contrast, the basic characteristics were preserved in the thin film prepared from the PFV-6moct aggregate (CHCl₃/MeOH); the film showed high both g_CD and g_CPL values close to those in the original aggregate.

中文翻译：

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溶液中带有手性烷基侧链的所有-反式-聚（9,9-二烷基芴-2,7-亚乙烯基）的圆二色性（CD）和圆偏振发光（CPL）光谱中符号和量级的明显手性中心依赖性，骨料和薄膜

聚（9,9-二烷基芴-2,7-乙烯基）[PFVs，（S）-3-甲基戊基（3mpe），（S）-4-甲基己基（4mhex），（S）-5-甲基庚基（5mhep），（S）-6-甲基辛基（6moct）和（S）-3,7-二甲基辛基（dmo）]朝向聚集诱导的圆二色性（AICD）和圆偏振发光（AICPL ）和溶液/薄膜中的CD / CPL光谱已被探索。的（所有-反式）PFV样品具有相似的共轭重复单元的含有明确定义的（乙烯基）端基通过使用钌催化剂的无环二烯烃易位聚合制备。PFV骨料，原位制备在CHCl ₃ / MeOH的混合溶液中，显示出清晰的CD信号归因于AICD，而这些样品在CHCl ₃溶液中显示出CD沉默。绝对量（g _CD值）受手性侧链的影响（不遵守奇偶规则），并以3mpe，5mhep <4mhex <dmo <6mcot的顺序增加。6-oct和dmo聚集体均显示归因于AICPL的清晰CPL信号，而其他聚集体的信号不明显。的λ_最大值在UV-vis光谱的红移，这取决于种烷基侧链的由于形成的值Ĵ型聚集体。这些结果表明，旋光性聚集体采用由通过链缠结的互聚物相互作用引起的某些螺旋超分子有序结构。滴延流延薄膜（由CHCl ₃溶液制备）中的g _CD值低于聚集体中的g _CD值，并且其值以5mhep，dmo ＜4mhex，6mcot ＜3mpe的顺序增加。_最大λ紫外可见光谱中的值发生红移，但不受侧链的影响。这些结果表明，由聚集体和膜形成的超分子结构是不同的，并且膜中的形成可以由互聚物π-堆垛诱导。相反，在由PFV-6分子聚集体（CHCl ₃ / MeOH）制得的薄膜中保留了基本特性。该膜显示出较高的g _CD和g _CPL值，接近原始聚集体中的值。