Metal–organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

Luminescent Metal–Organic Frameworks

Lanthanide-based luminescent hybrid materials.

Interpretation of europium(III) spectra

Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40th anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are dee...

Fundamentals and Catalytic Applications of CeO2-Based Materials

Advanced oxidation processes (AOPs), defined as those technologies that utilize the hydroxyl radical (·OH) for oxidation, have received increasing attention in the research and development of wastewater treatment technologies in the last decades. These processes have been applied successfully for the removal or degradation of toxic pollutants or used as pretreatment to convert recalcitrant pollutants into biodegradable compounds that can then be treated by conventional biological methods. The efficacy of AOPs depends on the generation of reactive free radicals, the most important of which is the hydroxyl radical (·OH). The authors summarize the formation reactions of ·OH and the mechanisms of pollutants degradation. They cover six types of advanced oxidation processes, including radiation, photolysis and photocatalysis, sonolysis, electrochemical oxidation technologies, Fenton-based reactions, and ozone-based processes. Controversial issues in pollutants degradation mechanism were discussed. They review t...

Advanced Oxidation Processes for Wastewater Treatment: Formation of Hydroxyl Radical and Application

A multicolored photoluminescent hybrid system based on lanthanide ions-doped metal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application.

Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange

Hybrid materials of SBA-15 functionalized by Tb3+ complexes of modified acetylacetone: Covalently bonded assembly and photoluminescence

Copolymer (MMA-co-MAL) of methyl methacrylate (MMA) and maleic anhydride (MAL) was prepared and grafted by 3-aminopropyltriethoxysilane (APES), which behaves as the structural precursor for functional bridge to assemble the covalently bonded systems through the coordination to rare earth ions (Eu 3+ , Tb 3+ ) with carboxylic groups of maleic anhydride. On the other hand, 1,10-phenanthroline (phen) is engaged in a second functional ligand to sensitize the luminescence of RE 3+ (rare earth ions) by intramolecular energy transfer process. Meanwhile, the cohydrolysis and copolycondensation processes happened between triethoxysilyl of modified copolymer (MMA-co-MAL-APES) and tetraethoxysilane (TEOS) with Si–O covalent bonds, resulting in the polymer-inorganic hybrids (phen-RE-MMA MMA-co-MAL-Si) exhibiting characteristic red or green emissions of Eu or Tb ions. Especially the luminescent quantum efficiencies of europium hybrid systems are estimated and discussed in detail.

Covalently bonded assembly and photoluminescent properties of rare earth/silica/poly(methyl methacrylate-co-maleic anhydride) hybrid materials

Tunable multi-color luminescence and white emission in lanthanide ion functionalized polyoxometalate-based metal–organic frameworks hybrids and fabricated thin films

A series of ternary rare earth (Eu(3+), Tb(3+)) complexes are covalently coated to the 3-aminopropyltriethoxysilane functionalized multi-walled carbon nanotube (MWCNT) by a simple in situ sol-gel method by the bifunctional silylated monomer TTA-Si and TAA-Si (TTA-Si and TAA-Si are 3-(triethoxysilyl)propylisocyanate (TEPIC) modified thenoyltrifluoroacetone (TTA) and trifluoroacetylacetone (TAA), respectively). The resulting materials are characterized by Fourier transform infrared spectra, scanning electronic microscope, transmission electron microscope, thermogravimetric analysis, ultraviolet visible diffused reflection measure, photoluminescence spectra, and X-ray diffraction. The photoluminesce measurements indicated that these hybrids exhibit characteristic red and green luminescence originating from the corresponding ternary rare earth ion (Eu(3+), Tb(3+)). The luminescence quenching effect of MWCNT networks have been successfully restrained by coating a relatively thicker silica-oxygen-based organic-inorganic complex. Furthermore, the fluorescence lifetimes and emission quantum efficiencies of Eu(3+) hybrid materials are also determined.

Bing Yan

Papers

Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange

Hybrid materials of SBA-15 functionalized by Tb3+ complexes of modified acetylacetone: Covalently bonded assembly and photoluminescence

Covalently bonded assembly and photoluminescent properties of rare earth/silica/poly(methyl methacrylate-co-maleic anhydride) hybrid materials

Tunable multi-color luminescence and white emission in lanthanide ion functionalized polyoxometalate-based metal–organic frameworks hybrids and fabricated thin films

Multi-walled carbon nanotube-based ternary rare earth (Eu3+, Tb3+) hybrid materials with organically modified silica-oxygen bridge