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Updated: Dec 3, 2025
Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene
Published on: July 3, 2015
The first pentagonal-bipyramidal vanadium(III) complexes with a Schiff-base N3O2 pentadentate ligand: synthesis,
Tamara A Bazhenova1, Leokadiya V Zorina2, Sergey V Simonov2
1Institute of Problems of Chemical Physics, RAS, Chernogolovka 142432, Russia. bazhen@cat.icp.ac.ru yagubski@icp.ac.ru.
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.
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