Black Alexander W, Bartlett Philip N
School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK.
Phys Chem Chem Phys. 2022 Apr 6;24(14):8093-8103. doi: 10.1039/d2cp00696k.
Weakly coordinating solvents, such as dichloromethane, have been shown to be attractive for the electrodeposition of functional p-block compound and alloy semiconductors for electronic device applications. In this work the use of solvent descriptors to define weakly coordinating solvents and to identify new candidates for electrochemical applications is discussed. A set of solvent selection criteria are identified based on Kamlet and Taft's π*, and parameters: suitable solvents should be polar (π* ≥ 0.55), aprotic and weakly coordinating ( and ≤ 0.2.). Five candidate solvents were identified and compared to dichloromethane: trifluorotoluene, -dichlorobenzene, -fluorotoluene, chlorobenzene and 1,2-dichloroethane. The solvents were compared using a suite of measurements including electrolyte voltammetric window, conductivity, and differential capacitance, and the electrochemistry of two model redox couples (decamethylferrocene and cobaltocenium hexafluorophosphate). Ion pairing is identified as a determining feature in weakly coordinating solvents and the criteria for selecting a solvent for electrochemistry is considered. -dichlorobenzene and 1,2-dichloroethane are shown to be the most promising of the five for application to electrodeposition because of their polarity.
弱配位溶剂，如二氯甲烷，已被证明对于用于电子器件应用的功能性p区化合物和合金半导体的电沉积具有吸引力。在这项工作中，讨论了使用溶剂描述符来定义弱配位溶剂并识别电化学应用的新候选溶剂。基于Kamlet和Taft的π以及参数确定了一组溶剂选择标准：合适的溶剂应该是极性的（π≥0.55）、非质子性的且弱配位的（和≤0.2）。确定了五种候选溶剂并与二氯甲烷进行比较：三氟甲苯、邻二氯苯、对氟甲苯、氯苯和1,2 - 二氯乙烷。使用一系列测量方法对这些溶剂进行了比较，包括电解质伏安窗口、电导率和微分电容，以及两种模型氧化还原对（十甲基二茂铁和六氟磷酸钴鎓）的电化学。离子对被确定为弱配位溶剂中的一个决定性特征，并考虑了选择电化学溶剂的标准。由于其极性，邻二氯苯和1,2 - 二氯乙烷在这五种溶剂中显示出最有希望用于电沉积。
