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基于溶液处理的菲咯啉基 Co(II) 配合物设计的阻变存储器件中的氧化还原开关行为:实验和密度泛函理论研究。

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies.

机构信息

Department of Chemistry, Indian Institute of Technology Jodhpur, Rajasthan 342030, India.

Department of Physics, Indian Institute of Technology Jodhpur, Rajasthan 342030, India.

出版信息

Inorg Chem. 2023 Mar 13;62(10):4170-4180. doi: 10.1021/acs.inorgchem.2c04264. Epub 2023 Feb 27.

DOI:10.1021/acs.inorgchem.2c04264
PMID:36848532
Abstract

We herein report a novel square-planar complex [CoL], which was synthesized using the electronically interesting phenalenyl-derived ligand LH = 9,9'-(ethane-1,2-diylbis(azanediyl))bis(1-phenalen-1-one). The molecular structure of the complex is confirmed with the help of the single-crystal X-ray diffraction technique. [CoL] is a mononuclear complex where the Co(II) ion is present in the square-planar geometry coordinated by the chelating bis-phenalenone ligand. The solid-state packing of [CoL] complex in a crystal structure has been explained with the help of supramolecular studies, which revealed that the π···π stacking present in the [CoL] complex is analogous to the one present in tetrathiafulvalene/tetracyanoquinodimethane charge transfer salt, well-known materials for their unique charge carrier interfaces. The [CoL] complex was employed as the active material to fabricate a resistive switching memory device, indium tin oxide/CoL/Al, and characterized using the write-read-erase-read cycle. The device has interestingly shown a stable and reproducible switching between two different resistance states for more than 2000 s. Observed bistable resistive states of the device have been explained by corroborating the electrochemical characterizations and density functional theory studies, where the role of the Co metal center and π-conjugated phenalenyl backbone in the redox-resistive switching mechanism is proposed.

摘要

我们在此报告了一种新型的平面四方配合物[CoL],它是使用具有有趣电子性质的菲咯啉衍生配体 LH = 9,9'-(乙烷-1,2-二基双(氮杂二基))双(1-菲咯啉-1-酮)合成的。该配合物的分子结构通过单晶 X 射线衍射技术得到证实。[CoL]是一种单核配合物,其中 Co(II)离子处于正方形平面几何构型,由螯合双菲咯啉酮配体配位。借助超分子研究解释了[CoL]配合物在晶体结构中的固态堆积,结果表明,[CoL]配合物中存在的π···π堆积类似于四硫富瓦烯/四氰基醌二甲烷电荷转移盐中的堆积,这些盐是众所周知的具有独特电荷载流子界面的材料。将[CoL]配合物用作活性材料来制造电阻式开关存储器件,即氧化铟锡/CoL/Al,并通过写入-读取-擦除-读取循环进行了表征。该器件令人感兴趣的是,在超过 2000 秒的时间内,在两种不同电阻状态之间表现出稳定且可重复的切换。通过证实电化学特性和密度泛函理论研究,解释了器件的双稳定电阻状态,其中提出了 Co 金属中心和π共轭菲咯啉骨架在氧化还原电阻开关机制中的作用。

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