Designing Near‐Infrared and Visible Light Emitters by Postsynthetic Modification of Ln⁺³–IRMOF‐3

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 (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 acetoacet-

Building Light‐Emitting Metal‐Organic Frameworks by Post‐Synthetic Modification

“…The room‐temperature excitation spectra of IRMOF‐3, IRMOF‐3‐CM and IRMOF‐3‐PY (Figure ) display a broad band in the 240–425 nm range ascribed to the π‐π* transitions of the organic matrix . These bands, although with distinct profiles, are also present in Tb/Eu‐IRMOF‐3‐CM and Tb/Eu‐IRMOF‐3‐PY excitation spectra (Figure ) due to the common Ligand‐to‐Metal Charge Transfer (LMCT) process, so‐called, antenna effect .…”

“…One of the most attractive features of MOFs is the possibility of their post‐synthetic modification (PSM), particularly by the reaction with the organic linkers to produce materials with new functionalities. PSM allows the modification of Ln–MOFs while, in essence, preserving the main features of the parent framework . PSM requires the starting MOFs to have suitable functional groups (‐NH 2 , ‐CHO, ‐OH, ‐SH) accessible via the nanochannels, appropriate pore size, and the used reagents must be soluble in an appropriate solvent in order to be able to purify the functionalized solid MOF by simple washing …”

Curcumin@metal organic frameworks nano-composite for treatment of chronic toxoplasmosis

“…These unique properties making MOFs have application in a lot of areas. MOFs are not only used in catalysis [3], gas storage [4] separation [5], water treatment [6], fuel purification [7], light emitters [8][9][10] but also used in drug delivery and imaging applications [11]. To date, most studies have investigated the pathway associated with pain and severe complications; while nano MOFs for oral administration, a common and simpler route commonly used, remain unexplored.…”

Luminescent Nanothermometers Obtained by Post‐Synthetic Modification of Metal‐Organic Framework MIL‐68

“…Certain MOFs features, such as a high surface area, large pore volume and a widely tuneable composition make them promising materials for many applications including gas storage and separation, catalysis and photocatalysis, optical, and in the biomedical area . Recently, post‐synthetic modification, i.e., the modification of a MOF after its synthesis preserving the essential features of the framework structure, was used as a route to obtain light emitting materials via coordination of the parent MOF to a trivalent lanthanide ion (Ln 3+ ) . These materials have, among other, the ability to sense with high sensitivity certain metal ions in solution…”