Premium
Designing Near‐Infrared and Visible Light Emitters by Postsynthetic Modification of Ln +3 –IRMOF‐3
Author(s) -
Abdelhameed Reda M.,
Carlos Luis D.,
Rabu P.,
Santos Sérgio M.,
Silva Artur M. S.,
Rocha João
Publication year - 2014
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.201402789
Subject(s) - chemistry , lanthanide , luminescence , metal organic framework , fourier transform infrared spectroscopy , spectroscopy , infrared spectroscopy , inorganic chemistry , analytical chemistry (journal) , ion , chemical engineering , organic chemistry , materials science , physics , optoelectronics , adsorption , quantum mechanics , engineering
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 (Nd 3+ ) and visible (Eu 3+ and Tb 3+ ) 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 ( 1 H) and ( 13 C) 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, β‐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.