{"title":"The Role of Terminal Groups in Nonchiral Rod-Like Compounds on the Formation of Polar Fluids","authors":"Michał Czerwiński*, , , Mateusz Mrukiewicz, , , Mateusz Filipow, , , Damian Pociecha, , , Natalia Podoliak, , , Dalibor Repček, , , Monika Zając, , and , Dorota Węgłowska, ","doi":"10.1021/acs.chemmater.5c02109","DOIUrl":null,"url":null,"abstract":"<p >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.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"8077–8087"},"PeriodicalIF":7.0000,"publicationDate":"2025-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5c02109","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.5c02109","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
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.
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.