Duggan S Genevieve, Rabbani S M Gulam, Miró Pere
Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States.
Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States.
Inorg Chem. 2025 Mar 3;64(8):3790-3795. doi: 10.1021/acs.inorgchem.4c04759. Epub 2025 Feb 19.
Polyoxovanadate-alkoxides are a growing family of earth-abundant first-row transition metal polynuclear species highly promising for their tunable redox properties. The speciation and nucleation chemical space of these species is divided into two groups: 1) fully oxidized V(V) monomeric precursors that aggregate into Lindqvist-type clusters and 2) reduced V(IV) precursors forming cyclic structures. The nucleation of cyclic polyoxovanadate-alkoxides with varying alkyl chain lengths, the impact of the presence of templating anions, and their subsequent evolution to the Lindqvist-type congener were studied by using density functional theory. The evolution of cyclic polyoxovanadate-alkoxides to oxygen-vacant cluster structures was found to be endergonic, in agreement with previous experimental work. Moreover, the reactivity with traces of water in alcohol solvents was confirmed to be the main thermodynamic driving force toward the formation of the mixed-valent Lindqvist-type polyoxovanadate species.
多氧钒酸酯醇盐是一类不断发展的、富含地球元素的第一排过渡金属多核物种，因其可调的氧化还原性质而极具前景。这些物种的形态和成核化学空间分为两类：1）完全氧化的V(V)单体前体，聚集成林德奎斯特型簇；2）还原的V(IV)前体，形成环状结构。通过密度泛函理论研究了不同烷基链长度的环状多氧钒酸酯醇盐的成核、模板阴离子存在的影响以及它们随后向林德奎斯特型同系物的演化。发现环状多氧钒酸酯醇盐向氧空位簇结构的演化是吸热的，这与之前的实验工作一致。此外，已证实与醇类溶剂中痕量水的反应性是形成混合价林德奎斯特型多氧钒酸盐物种的主要热力学驱动力。
