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Probing the pore structure of a chiral periodic mesoporous organosilica using liquid crystals

机译:用液晶探测手性周期性介孔有机硅的孔结构

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Periodic mesoporous organosilicas (PMO) are prepared by the surfactant-templated condensation of bridged organosilsesquioxane monomers. By controlling the nature of the organic segment, the type of surfactant and the condensation conditions, one can control the physical and chemical properties of the resulting PMO and produce highly ordered porous structures with a periodicity on the nanometer scale. The development of chiral PMO materials has been of significant interest given their potential in heterogeneous asymmetric catalysis, chiral chromatography and non-linear optics. Characterization of the chirality of pore structures in these materials thus far has been achieved by indirect methods including polarimetry and solid-state circular dichroism. We report herein a general and convenient approach to probe directly the pore structure of chiral PMO materials based on their interactions with inexpensive liquid crystalline solvents, which result in the induction of measurable chiral properties in the nematic (N) and smectic A (SmA) phases of the liquid crystals. The templated co-condensation of a biphenylene organosilsesquioxane monomer and a chiral binaphthyl organosilsesquioxane monomer produced a new chiral PMO material that was investigated as dopant in two different liquid crystal hosts. Measurements of induced circular dichroism and helical pitch in the nematic phase of the cyanobiphenyl liquid crystal 5CB, and the measurement of an induced electroclinic effect in the SmA phase of the phenyl benzoate liquid crystal 9004 were carried out. The induced chiral properties measured in these experiments are consistent with chirality transfer taking place inside the pores, and suggest that the inner structure of the pores in the PMO material is indeed chiral.
机译:周期性介孔有机二氧化硅(PMO)是通过桥连的有机倍半硅氧烷单体的表面活性剂模板缩合制备的。通过控制有机链段的性质,表面活性剂的类型和缩合条件,人们可以控制所得PMO的物理和化学性质,并产生具有纳米级周期性的高度有序的多孔结构。鉴于手性PMO材料在非均相不对称催化,手性色谱和非线性光学领域的潜力,其开发受到了广泛的关注。迄今为止,这些材料中孔结构的手性的表征已通过间接方法完成,包括极化法和固态圆二色性。我们在此报告了一种通用便捷的方法,可基于手性PMO材料与廉价液晶溶剂的相互作用直接探查手性PMO材料的孔结构,从而导致向列(N)和近晶A(SmA)相中可测量的手性性质的诱导液晶。联苯有机倍半硅氧烷单体和手性双萘基有机倍半硅氧烷单体的模板共缩合产生了一种新的手性PMO材料,该材料在两种不同的液晶主体中作为掺杂剂进行了研究。进行了氰基联苯液晶5CB的向列相的感应圆二色性和螺距的测定,以及苯甲酸苯酯液晶9004的SmA相的感应电斜率的测定。在这些实验中测量的诱导的手性性质与在孔内部发生的手性转移一致,并且表明PMO材料中的孔的内部结构确实是手性的。

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