Origin of the Director Tilt in the Lyotropic Smectic C* Analog Phase: Hydration Interactions and Solvent Variations.

Origin of the Director Tilt in the Lyotropic Smectic C* Analog Phase: Hydration Interactions and Solvent Variations.
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溶致层列相*模拟相中导向倾斜的起源:水合相互作用和溶剂变化

DOI:
10.1002/cphc.201500673
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发表时间:
2016
期刊:
Chemphyschem : a European journal of chemical physics and physical chemistry
影响因子:
--
通讯作者:
F. Giesselmann
F. Giesselmann
中科院分区:
--
文献类型:
--
作者:
J. R. Bruckner;F. Knecht;F. Giesselmann

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最近发现的指向矢倾斜的起源和长程相关性 相,这是热致近晶C*(SmC*)液晶相的溶致类似物,进行了研究。 偏振微拉曼光谱揭示了在晶体中的指向矢倾斜, 相源自表面活性剂分子的芳族2-苯基嘧啶核的倾斜。倾斜角的光学测量表明,其大小随着溶剂浓度的增加而减小,这表明倾斜方向的长程层间相关性随着溶剂层厚度的增加而减小。研究了四种不同溶剂(水、甲酰胺、N-甲基甲酰胺、N,N-二甲基甲酰胺)的相图,表明 相仅与那些表现出氢键密集网络的溶剂形成。这一观察结果表明,这些氢键网络在相邻表面活性剂层之间的指向矢倾斜的长程相关性中起着至关重要的作用。为了验证这一假设,研究了具有氘代溶剂的混合物,表明在氘代溶剂中的倾斜角 通过溶剂的氢键网络的这种改变,相确实减少了。
The origin and long‐range correlation of the director tilt in the recently discovered phase, which is the lyotropic analog of the thermotropic smectic C* (SmC*) liquid crystalline phase, are investigated. Polarized micro‐Raman spectroscopy reveals that the director tilt in the phase originates from a tilting of the aromatic 2‐phenylpyrimidine cores of the surfactant molecules. Optical measurements of the tilt angle show that its magnitude decreases with increasing solvent concentration, suggesting that the long‐range inter‐lamellar correlation of the tilt directions is reduced at increasing thickness of the solvent layers. The phase diagrams with four different solvents (water, formamide,N‐methylformamide,N,N‐dimethylformamide) are investigated, showing that the phase is only formed with those solvents that exhibit a dense network of hydrogen bonds. This observation suggests that these hydrogen bond networks play an essential role in the long‐range correlation of the director tilt between adjacent surfactant layers. To verify this assumption, mixtures with deuterated solvents are investigated, showing that the tilt angle in the phase is indeed reduced by this modification of the solvent′s hydrogen bond network.
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