Weakly coordinating solvents are of interest for the electrodeposition of p-block semiconductors for application in electronic devices. p-block complexes typically have weakly coordinated ligands that are easily displaced, making them incompatible with strongly Lewis basic solvents. In this work we use electrochemical measurements at microelectrodes to study diffusion in weakly coordinating solvents. Diffusion coefficients of the metallocenes decamethylferrocene, decamethylferrocenium hexafluorophosphate, cobaltocenium hexafluorophosphate, and the electrodeposition precursors tetrachloroantimonate(III) and tetrachlorobismuthate(III) were measured. The values are analysed using the modified Stokes-Einstein equation and compared with the theoretical upper, D_max, and lower, D_min, bounds of the diffusion coefficients. This approach allows the interpretation of D values, whilst avoiding dealing with some of the uncertainties associated with molecular size in the Stokes-Einstein equation. The neutral decamethylferrocene was found to obey the Stokes-Einstein equation whereas the charged metallocene species had values which were less than the theoretical minimum, which was attributed to a larger than expected particle size caused by ion pairing. The importance of considering the modifications of the Stokes-Einstein equation is also highlighted.

弱配位溶剂对于电沉积用于电子器件的 p 区半导体很有意义。p-嵌段配合物通常具有易于置换的弱配位体，使其与强路易斯碱性溶剂不相容。在这项工作中，我们使用微电极上的电化学测量来研究弱配位溶剂中的扩散。测量了茂金属十甲基二茂铁、十甲基二茂铁六氟磷酸盐、钴茂六氟磷酸盐和电沉积前体四氯锑酸盐(III)和四氯铋酸盐(III)的扩散系数。使用修改后的斯托克斯-爱因斯坦方程分析这些值，并与理论上限D _max和下限D进行比较_min，扩散系数的界限。这种方法可以解释D值，同时避免处理与斯托克斯-爱因斯坦方程中的分子大小相关的一些不确定性。发现中性十甲基二茂铁遵守斯托克斯-爱因斯坦方程，而带电茂金属物质的值小于理论最小值，这归因于离子配对引起的大于预期的粒径。还强调了考虑修改斯托克斯-爱因斯坦方程的重要性。