The Role of Terminal Groups in Nonchiral Rod-Like Compounds on the Formation of Polar Fluids

IF 7 2区 材料科学 Q2 CHEMISTRY, PHYSICAL
Michał Czerwiński*, , , Mateusz Mrukiewicz, , , Mateusz Filipow, , , Damian Pociecha, , , Natalia Podoliak, , , Dalibor Repček, , , Monika Zając, , and , Dorota Węgłowska, 
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Abstract

The emergence of ferroelectric mesophases in nonchiral liquid crystals (LCs) has sparked fundamental interest in the molecular mechanisms governing polarity. In this study, we investigate how terminal molecular groups influence the formation and stability of polar phases by analyzing six compounds from three homologous series. Specifically, we compare synthesized homologues with a nitro group, which predominantly exhibit polar mesophases, to previously reported structurally related analogs containing either a cyano group or a fluorine atom as a terminal fragment. Density functional theory calculations provide insights into electronic surface potential (ESP) distributions, revealing alternating regions of positive and negative charge density along the molecular axis, consistent with Madhusudana’s model of polar phase stabilization. We propose the ESP-derived parameter quantifying terminal electrostatic charge, revealing a direct correlation between the negative-to-positive charge ratio at the molecular termini and the formation of ferroelectric or antiferroelectric mesophases. To validate this hypothesis, we analyze the molecular structure–mesomorphic behavior relationship of other known nonchiral compounds that exhibit polar phases, demonstrating the critical role of terminal groups in determining mesophase polarity. Our findings enhance the understanding of the molecular origins of ferroelectricity in nonchiral LCs, paving the way for the rational design of next-generation functional polar soft materials.

非手性棒状化合物中末端基团在极性流体形成中的作用
非手性液晶(LCs)中铁电中间相的出现引起了人们对控制极性的分子机制的基本兴趣。在本研究中,我们通过分析来自3个同源系列的6个化合物,研究了末端分子基对极性相形成和稳定性的影响。具体来说,我们比较了合成的具有硝基的同源物,主要表现为极性中间相,与先前报道的结构相关的类似物含有氰基或氟原子作为末端片段。密度泛函理论计算提供了对电子表面电位(ESP)分布的深入了解,揭示了沿分子轴的正负电荷密度交替区域,与Madhusudana的极性相稳定模型一致。我们提出了用esp衍生的参数来量化末端静电电荷,揭示了分子末端负电荷与正电荷比与铁电或反铁电中间相的形成之间的直接关系。为了验证这一假设,我们分析了其他已知的具有极性相的非手性化合物的分子结构-亚形态行为关系,证明了末端基团在决定中间相极性中的关键作用。我们的发现增强了对非手性lc中铁电性分子起源的理解,为下一代功能极性软材料的合理设计铺平了道路。
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来源期刊
Chemistry of Materials
Chemistry of Materials 工程技术-材料科学:综合
CiteScore
14.10
自引率
5.80%
发文量
929
审稿时长
1.5 months
期刊介绍: The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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