Maruyama Yuto, Harano Koji, Kanai Hayato, Ishida Yasuhiro, Tanaka Hiroki, Sugiura Shinya, Maeda Hiromitsu
Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University, Kusatsu, 525-8577, Japan.
Center for Basic Research on Materials, National Institute for Materials Science, Tsukuba, 305-0044, Japan.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415135. doi: 10.1002/anie.202415135. Epub 2024 Nov 6.
In this study, a new assembly strategy for lyotropic chromonic liquid crystals (LCLCs) is proposed using π-π interactions, mainly comprising electrostatic and dispersion forces, between charged π-electronic systems to form stacking structures supported by the hydration of triethylene glycol (TEG) units. The meso-TEG-aryl-substituted porphyrin Au complex, an amphiphilic π-electronic cation, showed diverse states and assembly modes in ion pairs depending on the coexisting counteranions. The PCCp ion pair formed a hexagonal columnar (Col) LC phase based on a charge-by-charge assembly, suggesting the formation of an ordered arrangement of charged π-electronic systems through π-π interactions, with reduced interactions between the TEG chains. Furthermore, in the presence of water, LCLC behavior in the Col and nematic columnar phases according to the amount of water were observed for the PCCp ion pair as a result of π-π interactions. Magnetic-field-induced orientation of the charge-by-charge columnar structures upon dehydration was observed. Furthermore, single-stranded charge-by-charge columnar structures, as components of the LCLCs, were observed using transmission electron microscopy (TEM).
在本研究中，提出了一种用于溶致变色液晶（LCLC）的新组装策略，该策略利用带电π电子系统之间的π-π相互作用（主要包括静电力和色散力）来形成由三甘醇（TEG）单元水合作用支持的堆叠结构。介观TEG-芳基取代的卟啉金配合物是一种两亲性π电子阳离子，根据共存的抗衡阴离子，在离子对中表现出不同的状态和组装模式。PCCp离子对基于逐电荷组装形成了六方柱状（Col）液晶相，这表明通过π-π相互作用形成了带电π电子系统的有序排列，同时TEG链之间的相互作用减弱。此外，在有水存在的情况下，由于π-π相互作用，观察到PCCp离子对在Col相和向列柱状相中的LCLC行为随水量的变化。观察到脱水时逐电荷柱状结构的磁场诱导取向。此外，使用透射电子显微镜（TEM）观察到了作为LCLC组件的单链逐电荷柱状结构。
