Perez Alexia Rivera, Amjad Romina, Guzman Maria Cedeno, Constanza Cassandra, Juarez Yaisa, Miller Gwynneth, Cooper Courtney, Arnet Nicholas A
Department of Physical and Life Sciences, Nevada State University, Henderson, Nevada 89002-9455, United States.
J Electrochem Soc. 2024;171(10). doi: 10.1149/1945-7111/ad83f9. Epub 2024 Oct 15.
Seven acetylacetonate (acac) metal complexes ranging from early transition metals to post-transition metals were examined by cyclic voltammetry in acetonitrile (MeCN), dichloromethane (DCM), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and dimethylformamide (DMF). The electronic potential of any observed redox events is reported along with an analysis of the reversibility of those events across a range of scan rates. Group 8 compounds Fe(acac) Ru(acac) showed at least quasi-reversible reductions across all solvents while Ru(acac) also featured a reversible oxidation. The early and post-transition compounds VO(acac), Ga(acac) and In(acac) exhibited irreversible reductions, while TiO(acac) showed no redox activity within the examined potential ranges. Mn(acac) featured an oxidation that showed solvent-dependent reversibility, and a reduction that was irreversible in all examined solvents. DFT calculations indicated minimal solvent effects on the HOMO-LUMO gap for the majority of compounds, but a significant effect was observed for Ru(acac). This study serves as a valuable initial step for further examination of acetylacetonate metal complexes for applications as electrochemical internal standards, nanoparticle precursors, and electrocatalysts.
通过循环伏安法在乙腈（MeCN）、二氯甲烷（DCM）、四氢呋喃（THF）、二甲基亚砜（DMSO）和二甲基甲酰胺（DMF）中研究了七种从早期过渡金属到后过渡金属的乙酰丙酮（acac）金属配合物。报告了任何观察到的氧化还原事件的电势，并分析了这些事件在一系列扫描速率下的可逆性。第8族化合物Fe(acac)₃、Ru(acac)₃在所有溶剂中都至少表现出准可逆还原，而Ru(acac)₃还具有可逆氧化。早期和后过渡化合物VO(acac)₂、Ga(acac)₃和In(acac)₃表现出不可逆还原，而TiO(acac)₂在所研究的电势范围内没有氧化还原活性。Mn(acac)₃的氧化表现出溶剂依赖性可逆性，而还原在所有研究的溶剂中都是不可逆的。密度泛函理论计算表明，大多数化合物的溶剂对最高占据分子轨道-最低未占据分子轨道（HOMO-LUMO）能隙的影响最小，但Ru(acac)₃观察到显著影响。这项研究是进一步研究乙酰丙酮金属配合物作为电化学内标、纳米颗粒前体和电催化剂应用的有价值的第一步。
