Crystal and electronic structures and magnetic susceptibility of the photochemically prepared layered vanadyl phosphate Na(VO)2(PO4)2·4H2O†
Abstract
Prolonged photolysis of aqueous solutions containing Na3VO4, NaH2PO4, and O π* orbital at the opposite VIV, which is possible when both distances of (O
)V
⋯
V(
O) and (O
)V
⋯
O(
V) are short (≈4.55 and ≈4.36 Å, respectively). Otherwise, an antiferromagnetic property due to the superexchange interaction between magnetic dxy orbitals at both VIV is operative. The results of extended Hückel (EH) calculations for a fragment model [V8P8O40]4− (with VIV/VV = 1/1) support a variety of magnetic interactions of the unpaired electron at VIV in the V–P–O layer consisting of the retracted-chair V(OPO)2V rings.