Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing −CONHC14H29 Chains at 500 K,The Journal of Physical Chemistry C

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Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing −CONHC14H29 Chains at 500 K
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2019-08-30 , DOI: 10.1021/acs.jpcc.9b03866
Jianyun Wu ₁ , Takashi Takeda _{1,

2} , Norihisa Hoshino _{1,

2} , Yasutaka Suzuki ₃ , Jun Kawamata ₃ , Tomoyuki Akutagawa _{1,

2}

Affiliation

Optical properties of porphyrin derivatives were used to fabricate an artificial light-harvesting system. The introduction of a N–H···O═ hydrogen-bonding alkylamide chain (−CONHC_nH_2n+1) into a functional π-system is among the useful approaches to design multifunctional supramolecular assemblies. The tetraphenylporphyrin derivative bearing four −CONHC₁₄H₂₉ chains (1) shows the successive and reversible phase transition behavior of S1–S2 at 338 K, S2–Col_r at 444 K, and Col_r–I (isotropic liquid) at 564 K, where a fluidic discotic rectangular columnar (Col_r) liquid crystal phase was observed in a wide temperature range of 444–564 K before melting. The one-dimensional columnar molecular assembly of (1)_∞ was constructed using a simultaneous operation of N–H···O═ hydrogen-bonding and π-stacking interactions. Temperature (T)- and frequency (f)-dependent dielectric constants of 1 indicated characteristic dielectric enhancement at higher-T and lower-f conditions above 500 K because of the thermally activated motional freedom of the polar N–H···O═ hydrogen-bonding unit in the Col_r phase. The polarization–electric field (P–E) curves at f = 0.1 Hz clearly indicated ferroelectric hysteresis behavior with a remanent polarization (P_r) of 1 μC cm^–2 and a coercive electric field (E_c) of 2 V μm^–1 at 503 K. The stable operation of the high-T ferroelectrics at approximately 500 K facilitates the potential application of a memory device in a high-T environment.

中文翻译：

四苯基卟啉衍生物轴承-CONHC14H29链在500 K时的铁电性

卟啉衍生物的光学性质用于制造人工光收集系统。将N–H··O═氢键烷基酰胺链（-CONHC _n H _{2 n +1}）引入功能性π系统是设计多功能超分子组装的有用方法之一。带有四个-CONHC ₁₄ H ₂₉链的四苯基卟啉衍生物（1）显示338 K时S1-S2、444 K时S2-Col _r和564 K时Col _r- I（各向同性液体）的相继可逆相变行为，其中流体盘状矩形柱状（Col _r）在熔化之前，在444–564 K的宽温度范围内观察到液晶相。（1）_∞的一维柱状分子组装体是通过同时进行N–H···O═氢键键合和π堆积相互作用而构造的。温度（T）和频率（f）相关的介电常数为1表示在500 K以上的较高T和较低f条件下，由于极性N–H···O═的热激活运动自由度，介质介电增强Col _r相中的氢键单元。极化电场（P – E）在˚F = 0.1赫兹清楚地表明与剩余极化（电滞行为P _{- [R} 1μC厘米）^-2和矫顽电场（ë _Ç）2的V微米^-1在503 K.所述高的稳定运行Ť大约500 K的铁电介质有助于在高T环境中潜在地应用存储设备。

更新日期：2019-08-30

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