Jean-Claude Bunzli - Structural and luminescent properties of micro- and nanosized particles of lanthanide terephthalate coordination polymers

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  Daiguebonne,C., Kerbellec,N., Guillou,O., Bunzli,J.C., Gumy,F.,   Catala,L., Mallah,T., Audebrand,N., Gerault,Y., Bernot,K.,   Calvez,G. Inorganic Chemistry 2008  47 (9) 3700-3708

  Abstract: Reaction in water between rare earth   ions (Ln = Y, La-Tm, except Pm) and the sodium salt of   terephthalic acid leads to a family of lanthanide-based   coordination polymers of general formula   [Ln(2)(C8H4O4)(3)(H2O)(4)](n) with Ln = La-Tm or Y. The   isostructurality of the compounds with the previously reported   Tb-containing polymer is ascertained on the basis of their X-ray   powder diffraction diagrams. The coordination water molecules can   be reversibly removed without destroying the crystal structure   for compounds involving one of the lighter lanthanide ions   (La-Eu). For compounds involving one of the heavier lanthanide   ions (Tb-Tm) or yttrium, a structural change occurs during the   drying process. X-ray diffraction data show this new anhydrous   phase corresponding to the linking of pairs of Er(III) ions   through mu-carboxylate bridges, Porosity profiles calculated for   the anhydrous phases of Tb(III) and Er(III) show the presence of   channels with very small sections. The luminescent properties of   all the compounds have been recorded and the two most luminescent   polymers, namely, the europium- and the terbium-containing ones,   have been studied in more detail. Tb(ill)-containing compounds   display large quantum yields, up to 43%. Polyvinylpyrrolidone   nanoparticles doped with [Ln(2)(C8H4O4)(3)(H2O)(4)](n) (Ln = Eu,   Tb, Er) have also been synthesized and characterized. The   encapsulation of the coordination polymers results in somewhat   reduced luminescence intensities and lifetime, but the   nanoparticles can be dispersed in water and remain unchanged in   this medium for more than 20 h

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