Decoding the role of encapsulated ions in the electronic and magnetic properties of mixed-valence polyoxovanadate capsules {X@V22O54} (X = ClO4-, SCN-, VO2F2-): a combined theoretical approach.
Decoding the role of encapsulated ions in the electronic and magnetic properties of mixed-valence polyoxovanadate capsules {X@V22O54} (X = ClO4-, SCN-, VO2F2-): a combined theoretical approach.
复制标题
DOI：
10.1039/c8cp02669f
复制
发表时间：
2018-07
期刊：
影响因子：
--
通讯作者：
A. Notario-Estévez;P. Kozłowski;Oliver Linnenberg;C. de Graaf;X. López;K. Monakhov
中科院分区：
文献类型：
--
作者：
A. Notario-Estévez;P. Kozłowski;Oliver Linnenberg;C. de Graaf;X. López;K. Monakhov
通过密度泛函理论和有效哈密顿量计算两种理论方法评估了具有抗磁性 (X =) ClO4- (Td, 1) 和 SCN- (C∞v, 2) 模板阴离子的混合价主客体多氧钒酸盐 {X@VO54} 的电子结构和磁性。将结果与 X = VO2F2- (C2v, 3) 的该家族的另一个成员获得的结果进行比较（参见 P. Kozłowski 等人, Phys. Chem. Chem. Phys., 2017, 19, 29767-29771），还获得了补充数据。结果表明，X 客体阴离子强烈影响系统的电子和磁性，导致钒的各种价态并改变 V-O-V 交换相互作用。我们的研究结果与现有的实验数据一致并对其进行了阐明（参见 K. Y. Monakhov 等人, Chem. - Eur. J., 2015, 21, 2387-2397）。
The electronic structure and magnetism of mixed-valence, host-guest polyoxovanadates {X@VO54} with diamagnetic (X =) ClO4- (Td, 1) and SCN- (C∞v, 2) template anions are assessed by means of two theoretical methods: density functional theory and effective Hamiltonian calculations. The results are compared to those obtained for another member of this family with X = VO2F2- (C2v, 3) (see P. Kozłowski et al., Phys. Chem. Chem. Phys., 2017, 19, 29767-29771), for which complementary data are also acquired. It is demonstrated that the X guest anions strongly influence the electronic and magnetic properties of the system, leading to various valence states of vanadium and modifying V-O-V exchange interactions. Our findings are concordant with and elucidate the available experimental data (see K. Y. Monakhov et al., Chem. - Eur. J., 2015, 21, 2387-2397).