The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I2 per 1 mol of Ni(II)(pz)[Ni(II)(CN)4] in solution.

Hybrid nanocomposites based on nanoparticles with the Hofmann-type structure Ni II (pz)[Ni II (CN) 4 ] (where pz ¼ pyrazine) confined into mesoporous silica or porous glass pearls were synthesised by sequential coordination of the molecular precursors into the pores of the functionalized matrices. Infrared (IR) and UV/Visible (UV-Vis) spectroscopy, powder X-ray diffraction (PXRD), and transmission electron microscopy (TEM) reveal the presence of uniformly-sized spherical Ni II (pz)[Ni II (CN) 4 ] nanoparticles of 3-6 nm, which are homogeneously dispersed into the matrices. These nanocomposites are able to efficiently capture iodine from cyclohexane solutions with a maximum sorption capacity of 1.75 mmol per g of material. A particular emphasis is given on the mechanism of iodine sorption as well as on the sorption cycling ability of the materials.

A series of thermally stable Hofmann-type clathrate structures with the general formula M(pz)[M'(CN)4], where M and M' are bivalent metal ions M(II) = Ni(II), Co(II), M(II)' = Ni(II), Pd(II), Pt(II), and pz is the pyrazine bidentate ligand, was synthesized and investigated for the efficient entrapment of iodine (I2) in solution and in the gas phase. Iodine-containing clathrates thus prepared were analysed to determine the saturation capacity, thermal stability, guest-induced structural changes of the clathrate's lattice and the nature of the confined iodine according to the chemical composition of the host structure. An efficient confinement of about 1 I2 per unit cell is observed for the series of clathrates with the Ni(II) and Pd(II) ions in the square planar position whatever the bivalent metal ion in the octahedral position. Specific responses in the lattice adjustment are detected for Co(II) in the octahedral and Pd(II) in the square planar positions.

Prussian blue (PB) and its analogues on the nanometric scale are exciting nano-objects that combine the advantages of molecular-based materials and nanochemistry. Herein, we demonstrate that ultra-small PB nanoparticles of 2-3 nm can be easily labelled with radioactive (201)Tl(+) to obtain new nanoprobes as radiotracers for 201-thallium-based imaging.

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