Nanoscale Effects in One‐Dimensional Columnar Supramolecular Ferroelectrics

Abstract

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Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains

“…The addition of a small amount of a similar hydrogen-bonding Col h liquid crystal usually supressed the ferroelectric response. 68,69 There was no ferroelectric response from the Col h phase of 1, while the introduction of 1 into the ferroelectric 3BC domain gave rise to PÀE hysteresis curves. The remanent polarisation (P r ) of 3BC at 353 K (f ¼ 1 Hz) was P r ¼ 1.1 mC cm À2 (Fig.…”

“…The rst is a homogeneous random mixing state without domain separation, and the second is an inhomogeneous domain-separated mixing state. 68,69 The mixing with and without domain separation can be distinguished by the DSC and PXRD proles of the Col h phase. When the two different hydrogen-bonded columns of (1) N and (3BC) N can coexist in the same Col h phase, interestingly, both the ionic channel and ferroelectric chain coexist.…”

“…The two different hydrogen-bonding orientations (]O/N-HÀ and -N-H/O]) along the p-stacking axis can transform into each other under the application of an outer electric eld. [33][34][35][36][37] Another type of interesting molecular system with a selective ion recognition ability has been extensively designed with crown ether derivatives for application in phase-transfer catalysis, ion separation, ion sensing, and ion transport in the solution phase. 38 The chemical designs of the pore environment such as [12]crown-4, [15]crown-5, and [18]crown-6 are useful because of their high affinity to Li + , Na + , and K + ions.…”

Simple molecular ferroelectrics:N,N′-dialkyl-terephthalamide derivatives in the solid phase

“…The ferroelectric alkylamide unit can be introduced into a variety of functional p-molecules. For instance, the p-expanded pyrene [44][45][46] and tetrabenzoporphyrin 47 bearing four -CONHC 14 H 29 chains formed 1D ferroelectric hydrogen-bonding columns as well as a specific optical response simultaneously. Therefore, multifunctionality has been designed for various p-molecular systems using a rational design of hydrogen-bonding alkylamide chains.…”

Effective Na+-Binding Ability and Molecular Assembly of an Alkylamide-Substituted Penta(ethylene)glycol Derivative

“…Among them, the alkylamide group of −CONHC n H 2 n +1 is an interesting hydrogen-bonding structural unit for stabilizing the liquid crystal phase, as first demonstrated by Matsunaga et al for the discotic hexagonal columnar (Col h ) liquid crystal phase. − The effective intermolecular N–H···O hydrogen-bonding interaction enhances the order of molecular assembly in the intrinsic liquid state, leading to the appearance of the mesophase before melting to the liquid phase. For instance, a benzene derivative bearing three −CONHC n H 2 n +1 chains at the 1, 3, and 5-positions (3BC) forms the Col h liquid crystal phase by the aid of intermolecular N–H···O hydrogen-bonding interactions. , Interestingly, the application of electric field ( E ) along the hydrogen-bonding column of 3BC resulted in a ferroelectric response in the polarization–electric field ( P – E ) curve, wherein the dipole moment of each hydrogen-bonding chain was inverted by the application of outer E along the π-stack. − Further chemical design of the central core, from simple benzene to functional π-molecular systems such as pyrene and tetrabenzoporphyrin, has been utilized for fabricating multifunctional molecular materials. − For instance, a pyrene derivative bearing four −CONHC 14 H 29 chains exhibits ferroelectricity, fluorescence, and current-switching behavior. Most importantly, it can form multifunctional molecular assemblies such as organogels and nanofibers − The non π-planar 2,5-dimethylhelicene derivative bearing two −CONHC 14 H 29 chains also exhibited ferroelectricity, as evident from the P – E hysteresis curve.…”