Decoding the role of encapsulated ions in the electronic and magnetic properties of mixed-valence polyoxovanadate capsules {X@VO} (X = ClO, SCN, VOF): a combined theoretical approach

• Published in: Physical chemistry chemical physics : PCCP 2018, Vol.2 (26), p.17847-17858
• Main Authors: Notario-Estévez, Almudena, Koz owski, Piotr, Linnenberg, Oliver, de Graaf, Coen, López, Xavier, Monakhov, Kirill Yu
• Format: Article
• Language: English
• Subjects: Anions; Data acquisition; Decoding; Density functional theory; Diamagnetism; Electronic structure; Magnetic properties; Magnetism; Vanadium
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c8cp02669f

The electronic structure and magnetism of mixed-valence, host-guest polyoxovanadates {X@V IV/V 22 O 54 } with diamagnetic (X =) ClO 4 − ( T d , 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 = VO 2 F 2 − ( C 2v , 3 ) (see P. Koz owski 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). The magnetic states of polyoxovanadate host cages respond to inclusion of diamagnetic guest ions.