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|Designing Near-Infrared and Visible Light Emitters by Postsynthetic Modification of Ln(+3)-IRMOF-3
|Abdelhameed, Reda M.
Carlos, Luis D.
Santos, Sergio M.
Silva, Artur M. S.
LANTHANIDE COORDINATION POLYMERS
2ND-ORDER ZEEMAN TERMS
|WILEY-V C H VERLAG GMBH
|The postsynthetic modification of metal-organic frameworks is a promising new route for engineering optical centres and tuning the light emission properties of materials. Here, the postsynthetic modification of isoreticular metal-organic framework-3 (IRMOF-3) with ethyl oxalyl monochloride and ethyl acetoacetate followed by the chelation of trivalent lanthanide ions afforded efficient near-infrared (Nd3+) and visible (Eu3+ and Tb3+) light emitters. IRMOF-3 was used as an example owing to its highly porous crystalline structure and the presence of non-coordinating amino groups on the benzenedicarboxylate (bdc) linker, which are amenable to modification. The conversion of the amino groups was 100 and 65% for ethyl oxalyl monochloride and ethyl acetoacetate, respectively. The materials were characterised by elemental analysis, powder X-ray diffraction, optical and scanning electron microscopy, Fourier transform infrared spectroscopy, and solution (H-1) and (C-13) solid-state nuclear magnetic resonance spectroscopy. The solid-state luminescence properties of Ln-modified IRMOF-3 were investigated at room temperature. The presence of the bdc aromatic ring, beta-diketonates and oxamate enhanced the Ln(3+) sensitization through ligand-to-metal energy transfer. The magnetic behaviour of all compounds was further analysed. The spin-orbit coupling and zero-field splitting parameters were evaluated by fitting the experimental magnetic susceptibility to the analytical expressions for the free Ln(3+) ions.
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|Designing Near-Infrared and Visible Light Emitters by Postsynthetic Modification of Ln +3-IRMOF-3_10.1002ejic.201402789.pdf
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