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Photoluminescent Porous Modular Lanthanide–Vanadium–Organic Frameworks
Author(s) -
Rocha João,
Almeida Paz Filipe A.,
Shi FaNian,
Ferreira Rute A. S.,
Trindade Tito,
Carlos Luís D.
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900558
Subject(s) - lanthanide , chemistry , metal organic framework , crystallography , photoluminescence , thermogravimetry , europium , dodecahedron , sbus , inorganic chemistry , ion , organic chemistry , materials science , optoelectronics , adsorption
Modular mixed metal‐organic frameworks with lanthanide centres,M 4 [M 12 V 24 O 24 (OH) 8 (H 2 hedp) 8 (Hhedp) 16 (H 2 O) 64+ n ] · 88+ y (H 2 O) (M 3+ = Y 3+ , Ce 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Gd 3+ , Er 3+ ; H 5 hedp = etidronic acid), have been reported. The compounds have been prepared by (i) slow evaporation of the solvent to afford large single‐crystals of the Y 3+ , Ce 3+ and Er 3+ compounds and (ii) facile one‐pot synthesis (at ambient conditions) overnight to yield microcrystalline Y 3+ , Ce 3+ , Sm 3+ , Eu 3+ , Tb 3+ and Gd 3+ solids. Framework construction has been shown to be modular and based on the self‐assembly of cyclic trinuclear [V 3 O 3 (OH)(H 2 hedp)(Hhedp) 2 ] 6– anionic units with cationic {MO 8 } or {MO 9 } aqua‐based lanthanide complexes (with dodecahedral, square antiprismatic or tricapped trigonal prismatic coordination geometries), which gives rise to unprecedented trinodal networks (having 2‐ and 4‐connected nodes) with a total Schäfli symbol of {4.8 3 .10 2 } 2 {4 2 .8 4 }{8} 2 . The anionic charge of the networks is balanced by highly disordered trivalent lanthanide cations in the channels. The compounds have been studied by single‐crystal and powder X‐ray diffraction, vibrational spectroscopy (FTIR), thermogravimetry, optical and scanning electron microscopy and elemental analysis. The photoluminescence properties of selected compounds have been investigated. Intriguingly, the co‐existence of V 4+ and Eu 3+ cations in the same material allows the fine tuning of the photoluminescence emission from white to purplish‐blue, by changing the excitation wavelength.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)