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Title: | Designing Near-Infrared and Visible Light Emitters by Postsynthetic Modification of Ln(+3)-IRMOF-3 |
Author: | Abdelhameed, Reda M. Carlos, Luis D. Rabu, P. Santos, Sergio M. Silva, Artur M. S. Rocha, Joao |
Keywords: | METAL-ORGANIC FRAMEWORKS LANTHANIDE COORDINATION POLYMERS 2ND-ORDER ZEEMAN TERMS RARE-EARTH MAGNETIC-PROPERTIES PARAMAGNETIC-SUSCEPTIBILITY LUMINESCENCE PROPERTIES HYDROTHERMAL SYNTHESIS INORGANIC HYBRIDS COMPLEXES |
Issue Date: | 2014 |
Publisher: | WILEY-V C H VERLAG GMBH |
Abstract: | 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. |
Peer review: | yes |
URI: | http://hdl.handle.net/10773/20164 |
DOI: | 10.1002/ejic.201402789 |
ISSN: | 1434-1948 |
Publisher Version: | 10.1002/ejic.201402789 |
Appears in Collections: | CICECO - Artigos |
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File | Description | Size | Format | |
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Designing Near-Infrared and Visible Light Emitters by Postsynthetic Modification of Ln +3-IRMOF-3_10.1002ejic.201402789.pdf | 5.1 MB | Adobe PDF |
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