Nickel(II) 3,4;9,10-perylenediimide bis-phosphonate pentahydrate: a metal-organic ferromagnetic dye

The new metal-organic compound nickel(II) 3,4;9,10-perylenediimide bis-phosphonate pentahydrate, i.e. Ni(2)[(PDI-BP)(H(2)O)(2)]·3H(2)O (1), has been synthesized and its structural and magnetic properties have been studied. Reaction of 3,4;9,10-perylenediimide bis-phosphonate (PDI-BP, hereafter) ligand and nickel chloride in water resulted in the precipitation of a red and poorly crystalline solid (1). As the solid shows a poor crystalline organization of aggregates, the energy dispersive X-ray diffraction analysis (EDXD) technique has been used to obtain short-range order structural information of the single nanoaggregates by radial distribution function analysis. The overall structure of the compound is characterized by layers containing perylene planes shifted in the direction perpendicular to the stacking axes in such a way that only the outer rings overlap. The edges of the perylene planes are connected to the phosphonate groups through an imido group. The oxygen atoms of the [-PO(3)](2-) group and those of the water molecules are bonded to the nickel ions resulting in a [NiO(6)] octahedral coordination sphere. The Ni-O bond lengths are 0.21 ± 0.08 nm and the Ni-O-Ni angles of aligned moieties are 95 ± 2°. The oxygen atoms of the water molecules and the nickel atoms are nearly planar and almost perpendicular to the perylene planes forming chains of edge-sharing octahedra. The magnetic properties of (1) show the presence of intrachain ferromagnetic Ni-Ni interactions and a long-range ferromagnetic order below 21 K with a canting angle and with a spin glasslike behavior due to disorder in the inorganic layer. Hysteresis cycles show a coercive field of ca. 272 mT at 2 K that decreases as the temperature is increased and vanishes at ca. 20 K.