The first pentagonal-bipyramidal vanadium(III) complexes with a Schiff-base N3O2 pentadentate ligand

• Verfasst von: Bazhenova, Tamara A. [VerfasserIn]
• Verfasst von: Zorina, Leokadiya V. [VerfasserIn]
• Verfasst von: Simonov, Sergey V. [VerfasserIn]
• Verfasst von: Mironov, Vladimir S. [VerfasserIn]
• Verfasst von: Maximova, Olga V. [VerfasserIn]
• Verfasst von: Spillecke, Lena [VerfasserIn]
• Verfasst von: Koo, Changhyun [VerfasserIn]
• Verfasst von: Klingeler, Rüdiger [VerfasserIn]
• Verfasst von: Manakin, Yuriy V. [VerfasserIn]
• Verfasst von: Vasiliev, Alexander N. [VerfasserIn]
• Verfasst von: Yagubskii, Eduard B. [VerfasserIn]
• Titel: The first pentagonal-bipyramidal vanadium(III) complexes with a Schiff-base N3O2 pentadentate ligand
• Titelzusatz: synthesis, structure and magnetic properties
• Verf.angabe: Tamara A. Bazhenova, Leokadiya V. Zorina, Sergey V. Simonov, Vladimir S. Mironov, Olga V. Maximova, Lena Spillecke, Changhyun Koo, Rüdiger Klingeler, Yuriy V. Manakin, Alexander N. Vasiliev, Eduard B. Yagubskii
• E-Jahr: 2020
• Jahr: 05 Oct 2020
• Umfang: 12 S.
• Fussnoten: Gesehen am 18.07.2022 ; Im Titel sind die Zahlen "2" und "3" tiefgestellt
• Titel Quelle: Enthalten in: Dalton transactions
• Ort Quelle: London : Soc., 1972
• Jahr Quelle: 2020
• Band/Heft Quelle: 49(2020), 43, Seite 15287-15298
• ISSN Quelle: 1477-9234
• DOI: doi:10.1039/D0DT03092A
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 181072712X

Abstract

A series of three mononuclear pentagonal-bipyramidal V(III) complexes with the equatorial pentadentate N3O2 ligand (2,6-diacethylpyridinebis(benzoylhydrazone), H2DAPBH) in the different charge states (H2DAPBH0, HDAPBH1−, DAPBH2−) and various apical ligands (Cl−, CH3OH, SCN−) were synthesized and characterized structurally and magnetically: [V(H2DAPBH)Cl2]Cl·C2H5OH (1), [V(HDAPBH)(NCS)2]·0.5CH3CN·0.5CH3OH (2) and [V(DAPBH)(CH3OH)2]Cl·CH3OH (3). All three complexes reveal paramagnetic behavior, resulting from isolated S = 1 spins with positive zero-field splitting energy expected for the high-spin ground state of the V3+ (3d2) ion in a PBP coordination. Detailed high-field EPR measurements for compound 3 show that its magnetic properties are best described by using the spin Hamiltonian with the positive ZFS energy (D = +4.1 cm−1) and pronounced dimer-like antiferromagnetic spin coupling (J = −1.1 cm−1). Theoretical analysis based on superexchange calculations reveals that the long-range spin coupling between distant V3+ ions (8.65 Å) is mediated through π-stacking contacts between the planar DAPBH2− ligands of two neighboring [V(DAPBH)(CH3OH)2]+ complexes.