Cheng Feng, Wu Shuqi, Zheng Wenwei, Su Shengqun, Nakanishi Takumi, Xu Wenhuang, Sadhukhan Pritam, Sejima Hibiki, Ikenaga Shimon, Yamamoto Kaoru, Gao Kaige, Kanegawa Shinji, Sato Osamu
Institute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka Nishi-ku, Fukuoka, 819-0395, Japan.
Department of Physics, Okayama University of Science, Okayama, Japan.
Chemistry. 2022 Oct 21;28(59):e202202161. doi: 10.1002/chem.202202161. Epub 2022 Aug 24.
The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P2 ). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.
具有电子转移特性的配合物在极性空间群中结晶可诱导晶体在特定方向上的极化切换，这对传感器、存储器件和电容器的发展具有吸引力。不幸的是，在极性空间群中结晶的概率通常较低。注意到对映体纯的化合物在 Sohncke 空间群中结晶，本文报道了一种基于分子内电子转移和手性的非铁电极化切换晶体分子设计策略。此外，本文描述了一种带有对映体纯配体的单核价互变异构（VT）钴配合物的合成。对映体的引入使该配合物能够在极性空间群（P2 ）中结晶。晶体沿 b 轴方向的极化不会相互抵消，并且价互变转变伴随着极性晶体宏观极化的变化。在室温左右实现了通过电子转移的极化切换。
