Control of stoichiometry, size and morphology of inorganic polymers by template assisted coordination chemistry

Magnetism and Photomagnetism of Prussian Blue Analogue Nanoparticles Embedded in Porous Metal Oxide Ordered Nanostructures

“…Thus, either by reproducing or by adapting procedures described in the literature, various silica (SiO 2 ) matrices have been prepared to serve as host matrices for the synthesis of PBAs. These are powders generally composed of micrometre-sized grains with 2D hexagonal or wormlike organization of the pores, [37,38,[56][57][58] monoliths with 2D hexagonal, cubic, lamellar or wormlike organization of the pores [39,59] or films with 2D hexagonal organization of channels aligned perpendicular [60] or parallel [61] to the surface of the film. The films with the pores aligned parallel to the surface were obtained by evaporationinduced self-assembly (EISA) combined with spin-coating [61] whereas the films with the pores aligned perpendicular to the surface were obtained by self-assembly combined with electrochemical deposition.…”

“…Thus, we opted for (i) the synthesis of the coordination polymer within an inert nanoreactor made of oxide walls and free of any chemical species, and (ii) a nucleationgrowth process that can be implemented for any PBA and PBD. The strategy, which was developed step-by-step, [39,59,69,72,73] led to the optimized synthetic pathway described above (section 3.3): introduction of the first PBA precursor during the monolith preparation and subsequent introduction of the second precursor through a classical impregnation step. In order to fully confine the precipitation and to prevent PBA formation outside the porosity, a two-solvent approach is implemented for the impregnation step: the monolith is immersed in a hydrophobic solvent that is immiscible with the aqueous reactive solution and exhibits less affinity than the latter for the porosity.…”

“…The nanocomposites are composed of PBA nanoparticles (5 ± 1 nm) formed within the mesopores freed from the surfactant. [39,59,69,70] The characteristics of the oxide matrices and of the confined coordination polymer formed by the two-step introduction of the precursors within the pores are collected in Table 4.…”

“…Scheme of the unit cell for (a) an alkali-cation-free PBA, and (b) a PBA containing two alkali cations per cell. compounds, many efforts have thus been devoted to produce PBAs in various shapes and sizes: nanoparticles, [32][33][34][35][36][37][38][39] core-shell particles, [40][41][42] films [43][44][45] and wires, [46,47] thus also making them key compounds in the field of molecular nanomaterials.…”

“…The final material is composed of CoFe PBA nanoparticles (3-4 nm) wrapped in surfactant molecules within the MSU-type silica channels. [58] A different approach was used to prepare CoFe, [59,69] RbCoFe, [39,59,61,69,70] NiCr [59] and NiFe [70] PBA nanoparticles within the surfactant-free ordered mesopores of silica monoliths exhibiting 2D hexagonal, cubic, lamellar and wormlike organizations. Here the solvated metal ion PBA precursor is introduced within the silica channels during the synthesis of the silica matrix.…”