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Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-06-17 , DOI: 10.1021/jacs.3c01530 Wei-Jian Xu 1 , Mao-Fan Li 2 , Ana R Garcia 3 , Konstantin Romanyuk 4 , José M G Martinho 3 , Pavel Zelenovskii 1 , Alexander Tselev 4 , Luís Verissimo 1 , Wei-Xiong Zhang 2 , Xiao-Ming Chen 2 , Andrei Kholkin 4 , João Rocha 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-06-17 , DOI: 10.1021/jacs.3c01530 Wei-Jian Xu 1 , Mao-Fan Li 2 , Ana R Garcia 3 , Konstantin Romanyuk 4 , José M G Martinho 3 , Pavel Zelenovskii 1 , Alexander Tselev 4 , Luís Verissimo 1 , Wei-Xiong Zhang 2 , Xiao-Ming Chen 2 , Andrei Kholkin 4 , João Rocha 1
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The development of photo-responsive ferroelectrics whose polarization may be remotely controlled by optical means is of fundamental importance for basic research and technological applications. Herein, we report the design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)5(NO)] (1) (DMA = dimethylammonium, PIP = piperidinium) with potential phototunable polarization via a dual-organic-cation molecular design strategy. Compared to the parent non-ferroelectric (MA)2[Fe(CN)5(NO)] (MA = methylammonium) material with a phase transition at 207 K, the introduction of larger dual organic cations both lowers the crystal symmetry affording robust ferroelectricity and increases the energy barrier of molecular motions, endowing 1 with a large polarization of up to 7.6 μC cm–2 and a high Curie temperature (Tc) of 316 K. Infrared spectroscopy shows that the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. Specifically, the ground state with the N-bound nitrosyl ligand conformation can be reversibly switched to both the metastable state I (MSI) with isonitrosyl conformation and the metastable state II (MSII) with side-on nitrosyl conformation. Quantum chemistry calculations suggest that the photoisomerization significantly changes the dipole moment of the [Fe(CN)5(NO)]2– anion, thus leading to three ferroelectric states with different values of macroscopic polarization. Such optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization open up a new and attractive route to optically controllable macroscopic polarization.
中文翻译：
可逆光异构化金属亚硝基铁电体的分子设计
开发可通过光学手段远程控制偏振的光响应铁电体对于基础研究和技术应用具有重要意义。在此，我们报告了一种新型金属亚硝酰铁电晶体 (DMA)(PIP)[Fe(CN) 5 (NO)] ( 1 )（DMA = 二甲基铵，PIP = 哌啶鎓）的设计和合成，该晶体通过双有机阳离子分子设计策略。与母体非铁电体 (MA) 2 [Fe(CN) 5相比(NO)] (MA = 甲基铵) 材料在 207 K 发生相变，引入较大的双有机阳离子既降低了晶体对称性，提供了强大的铁电性，又增加了分子运动的能垒，赋予 1 向上的大极化至 7.6 μC cm –2和高居里温度 ( T c）的316 K。红外光谱表明亚硝酰基配体的可逆光异构化是通过光照射完成的。具体而言，具有N-结合亚硝酰基配体构象的基态可以可逆地转换为具有异亚硝基构象的亚稳态I（MSI）和具有侧向亚硝酰基构象的亚稳态II（MSII）。量子化学计算表明，光异构化显着改变了 [Fe(CN) 5 (NO)] 2–的偶极矩阴离子，从而导致具有不同宏观极化值的三种铁电态。这种通过光诱导亚硝酰键异构化实现不同铁电态的光学可及性和可控性，为光学可控宏观偏振开辟了一条新的、有吸引力的途径。
更新日期：2023-06-17
中文翻译：
可逆光异构化金属亚硝基铁电体的分子设计
开发可通过光学手段远程控制偏振的光响应铁电体对于基础研究和技术应用具有重要意义。在此，我们报告了一种新型金属亚硝酰铁电晶体 (DMA)(PIP)[Fe(CN) 5 (NO)] ( 1 )（DMA = 二甲基铵，PIP = 哌啶鎓）的设计和合成，该晶体通过双有机阳离子分子设计策略。与母体非铁电体 (MA) 2 [Fe(CN) 5相比(NO)] (MA = 甲基铵) 材料在 207 K 发生相变，引入较大的双有机阳离子既降低了晶体对称性，提供了强大的铁电性，又增加了分子运动的能垒，赋予 1 向上的大极化至 7.6 μC cm –2和高居里温度 ( T c）的316 K。红外光谱表明亚硝酰基配体的可逆光异构化是通过光照射完成的。具体而言，具有N-结合亚硝酰基配体构象的基态可以可逆地转换为具有异亚硝基构象的亚稳态I（MSI）和具有侧向亚硝酰基构象的亚稳态II（MSII）。量子化学计算表明，光异构化显着改变了 [Fe(CN) 5 (NO)] 2–的偶极矩阴离子，从而导致具有不同宏观极化值的三种铁电态。这种通过光诱导亚硝酰键异构化实现不同铁电态的光学可及性和可控性，为光学可控宏观偏振开辟了一条新的、有吸引力的途径。
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