Gulam Rabbani S M, Miró Pere
Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States.
Inorg Chem. 2023 Feb 6;62(5):1797-1803. doi: 10.1021/acs.inorgchem.1c03589. Epub 2022 Mar 28.
Polyoxovanadate-alkoxide clusters are a new class of electroactive species with applications in a wide variety of fields from redox catalysis to energy storage. Heterometallic installation in these species can be used to modulate the redox properties of polyoxovanadate-alkoxide clusters and thus their applications. However, the formation mechanism of heterometallic polyoxovanadate alkoxides during the solvothermal process is unknown, limiting our understanding regarding what thermodynamic driving forces and/or kinetic barriers are present in the heterometal insertion. Here, we present a computational study on the nucleation pathways of the iron-functionalized mixed-valent hexameric [VVO(μ-O)(μ-OCH)(FeCl)] polyoxovanadate-alkoxide cluster.
多氧钒酸盐 - 醇盐簇是一类新型的电活性物种，在从氧化还原催化到能量存储等广泛领域都有应用。在这些物种中引入杂金属可用于调节多氧钒酸盐 - 醇盐簇的氧化还原性质，进而影响其应用。然而，在溶剂热过程中杂金属多氧钒酸盐醇盐的形成机制尚不清楚，这限制了我们对杂金属插入过程中存在哪些热力学驱动力和/或动力学障碍的理解。在此，我们对铁功能化的混合价态六聚体[VVO(μ - O)(μ - OCH)(FeCl)]多氧钒酸盐 - 醇盐簇的成核途径进行了计算研究。
