Ferroelectricity and Phase Change Memory of Bis(tetradecylamide)-Substituted Benzene Derivatives
Ferroelectricity and Phase Change Memory of Bis(tetradecylamide)-Substituted Benzene Derivatives
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DOI：
10.1021/acs.jpcc.2c07343
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发表时间：
2023-01
期刊：
影响因子：
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通讯作者：
Ryohei Mizoue;Moeko Kawana;Takashi Takeda;Norihisa Hoshino;T. Akutagawa
中科院分区：
文献类型：
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作者：
Ryohei Mizoue;Moeko Kawana;Takashi Takeda;Norihisa Hoshino;T. Akutagawa
分子晶体中分子间的氢键、卤素-卤素、货车范德华力等相互作用导致了不同的相变行为和物理性质。双对十四酰胺取代的苯衍生物C14-TPA、C14-IPA和C14-PA进行了研究，发现前两种晶体在高温固相中具有铁电电滞回行为。合成了C14-XIPA衍生物，其中IPA分子5位上的X = CH 3、Cl、Br或I，研究了取代基X对分子组装体结构和物理性能的影响。H和CH 3取代的C14-IPA和C14-MeIPA形成了分子间酰胺型N-H···O-氢键相互作用占主导地位的结晶相，而卤素取代的C14-XIPA在从各向同性液体冷却时形成亚稳玻璃相。玻璃相的形成与−CONH-、−X和− CnH 2n +1单元之间的氢键、卤素-卤素和货车范德华相互作用之间的能量竞争有关。C14-XIPAs（X = Cl、Br或I）的玻璃-晶体相变在偏光显微镜下观察到折射率的变化，可用于相变存储。
Interplay between intermolecular interactions including hydrogen bonding, halogen–halogen, and van der Waals interactions in molecular crystals leads to diverse phase transition behaviors and physical properties. Bis(tetradecylamide)-substituted benzene derivatives, terephthalamide (C14-TPA), isophthalamide (C14-IPA), and phthalamide (C14-PA), were examined, and the electric field–polarization curves of the former two crystals indicated ferroelectric hysteresis behavior in high-temperature solid phases.C14-XIPAderivatives where X = CH3, Cl, Br, or I at the 5-position of the IPA molecule were synthesized, and the effects of substituent X on the molecular assembly structure and physical properties were investigated. H- and CH3-substitutedC14-IPAandC14-MeIPAformed a crystalline phase in which intermolecular amide-type N–H···O═ hydrogen-bonding interactions were dominant, whereas halogen-substitutedC14-XIPAsformed a metastable glass phase upon cooling from the isotropic liquid. The formation of the glass phase is associated with energy competition between hydrogen bonding, halogen–halogen, and van der Waals interactions among the −CONH–, −X, and −CnH2n+1units. The glass-crystal phase transition ofC14-XIPAs(X = Cl, Br, or I) changes the refractive index under polarized optical microscopic observation, which can be utilized for phase-change memory.