Directional Electron Transfer in Crystals of [CrCo] Dinuclear Complexes Achieved by Chirality-Assisted Preparative Method
Directional Electron Transfer in Crystals of [CrCo] Dinuclear Complexes Achieved by Chirality-Assisted Preparative Method
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DOI：
10.1021/jacs.6b05089
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发表时间：
2016-11-02
影响因子：
15
通讯作者：
Sato, Osamu
中科院分区：
文献类型：
--
作者：
Kanegawa, Shinji;Shiota, Yoshihito;Sato, Osamu
极化开关机构用于各种器件，如热释电传感器和存储器件。极化变化主要是由离子位移引起的。开发通过电子转移实现极化开关以提高运算速度的材料是一个挑战。我们设计了一种合成和晶体工程策略，能够选择性合成具有极性晶体结构的[CrCo]异金属双核配合物，其中极性变化源于co与配体之间的分子内电荷转移。偏振可以通过可见光照射和温度变化来调节。手性配体的引入对价互变异构化合物的成功极化开关至关重要。将Cr和Co配合物与对映纯手性配体混合，可选择性地形成伪对称的[CrCo]异质金属配合物。此外，左手手性配体优先与右手配体相互作用，使分子形成极性晶体结构。
The polarization switching mechanism is used in various devices such as pyroelectric sensors and memory devices. The change in polarization mostly occurs by ion displacement. The development of materials whose polarization switches via electron transfer in order to enhance operation speed is a challenge. We devised a synthetic and crystal engineering strategy that enables the selective synthesis of a [CrCo] heterometallic dinuclear complex with a polar crystal structure, wherein polarization changes stem from intramolecular charge transfer between co and the ligand. Polarization can be modulated both by visible-light irradiation and temperature change. The introduction of chiral ligands was paramount to the successful polarization switching in the valence tautomeric compound. Mixing Cr and Co complexes with enantiopure chiral ligands resulted in the selective formation of only pseudosymmetric [CrCo] heterometallic complexes. Furthermore, the left-handed chiral ligands preferentially interacted with their right-handed counterparts, enabling molecules to form a polar crystal structure.