Synthesis and structural investigation of iodine doped uranium diphthalocyanine-UPc2I2

Partially oxidized by iodine uranium(IV) diphthalocyanine, U(C32H16N8)2I2, (UPc2I2) was obtained by the direct reaction of pure powder uranium with 1,2-dicyanobenzene under a stream of iodine. The compound crystallizes in a space group P4/nnc of the tetragonal system with two molecules in a unit cell. The U atoms in the crystal are disordered onto two different crystallographic positions (2a and 2b) in ratio of 1:5. The crystal is composed of partially oxidized UPc2 units, which form a pseudo monodimensional stack along [001] direction. The stacks are surrounded by disordered chains of iodine, identified as I3 − ions by Raman spectroscopy. The EPR measurement exhibits a single signal at g=2.0013, the spin concentration (0.15 spins per UPc2 molecule) indicates spin–spin coupling between the monooxidized Pc− ring within the columns.