Metal-organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications. Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas. A very interesting and well-investigated topic is their optical emission properties and related applications. Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011. This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection. The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection.

We designed and synthesized a new luminescent metal-organic framework (LMOF). LMOF-241 is highly porous and emits strong blue light with high efficiency. We demonstrate for the first time that very fast and extremely sensitive optical detection can be achieved, making use of the fluorescence quenching of an LMOF material. The compound is responsive to Aflatoxin B1 at parts per billion level, which makes it the best performing luminescence-based chemical sensor to date. We studied the electronic properties of LMOF-241 and selected mycotoxins, as well as the extent of mycotoxin-LMOF interactions, employing theoretical methods. Possible electron and energy transfer mechanisms are discussed.

An important aspect in the research and development of white light-emitting diodes (WLEDs) is the discovery of highly efficient phosphors free of rare-earth (RE) elements. Herein we report the design and synthesis of a new type of RE-free, blue-excitable yellow phosphor, obtained by combining a strongly emissive molecular fluorophore with a bandgap modulating co-ligand, in a three-dimensional metal organic framework. [Zn6(btc)4(tppe)2(DMA)2] (btc = benzene-1,3,5-tricarboxylate, tppe = 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene, DMA = dimethylacetamide) crystallizes in a new structure type and emits bright yellow light when excited by a blue light source. It possesses the highest internal quantum yield among all RE-free, blue-excitable yellow phosphors reported to date, with a value as high as 90.7% (λex = 400 nm). In addition to its high internal quantum yield, the new yellow phosphor also demonstrates high external quantum yield, luminescent and moisture stability, solution processability, and color tunability, making it a promising material for use in phosphor conversion WLEDs.

Copper(I) iodide (CuI)-based inorganic-organic hybrid materials in the general chemical formula of CuI(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials' crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic-organic hybrid materials.

Metal organic frameworks (MOFs) are of enormous current interest not only because of their fundamental importance but also due to their great potential for possible applications in gas storage and separation, catalysis, imaging and sensing, to name a few. Recent studies on luminescent MOFs (LMOFs) in both bulk and nanoparticle forms have shown that these materials possess excellent luminescence emission properties that may be utilized to effectively detect high explosive substances. Developing highly sensitive, selective, fast-responding and fully reversible sensors for explosives' detection is in great demand for the homeland security, environmental safety and other humanitarian concerns. In this perspective article, we discuss the development, possible mechanism and future aspects of explosive sensing by LMOF materials.

We design a new yellow phosphor with high quantum yield by immobilizing a preselected chromophore into a rigid framework. Coating a blue light-emitting diode (LED) with this compound readily generates white light with high luminous efficacy. The new yellow phosphor demonstrates great potential for use in phosphor-converted white LEDs.

As one of the most rapidly evolving branches of solid-state lighting technologies, light emitting diodes (LEDs) are gradually replacing conventional lighting sources due to their advantages in energy saving and environmental protection. At the present time, commercially available white light emitting diodes (WLEDs) are predominantly phosphor based (e.g., a yellow-emitting phosphor, such as cerium-doped yttrium aluminum garnet or (YAG):Ce(3+), coupled with a blue-emitting InGaN/GaN diode), which rely heavily on rare-earth (RE) metals. To avoid potential supply risks of these elements, we have developed an inorganic-organic hybrid phosphor family based on I-VII binary semiconductors. The hybrid phosphor materials are totally free of rare-earth metals. They can be synthesized by a simple, low-cost solution process and are easily scalable. Their band gap and emission energy, intensity, and color can be systematically tuned by incorporating ligands with suitable electronic properties. High quantum efficiency is achieved for some of these compounds. Such features make this group of materials promising candidates as alternative phosphors for use in general lighting devices.

A systematic study is conducted on four microporous metal–organic framework compounds built on similar ligands but different structures, namely [Zn3(bpdc)3(bpy)]⋅4 DMF⋅H2O (1), [Zn3(bpdc)3(2,2′dmbpy)]⋅4 DMF⋅ H2O (2), [Zn2(bpdc)2(bpe)]⋅2 DMF (3), and [Zn(bpdc)(bpe)]⋅DMF (4) (bpdc=4,4′‐biphenyldicarboxylate; bpy=4,4′‐bipyridine; 2,2′dmbpy=2,2′‐dimethyl‐4,4′bipyridine; bpe=1,2‐bis(4‐pyridyl)ethane; DMF=N,N′‐dimethylformamide) to investigate their photoluminescence properties and sensing/detection behavior upon exposure to vapors of various aromatic molecules (analytes) including nitroaromatic explosives. The results show that all four compounds are capable of detecting these molecules in the vapor phase through fluorescence quenching or enhancement. Both electrochemical measurements and theoretical calculations are performed to analyze the analyte–MOF interactions, to explain the difference in signal response by different analytes, and to understand the mechanism of fluorescence quenching or enhancement observed in these systems. Interestingly, compound 3 also shows an emission frequency shift when exposed to benzene (BZ), chlorobenzene (ClBZ), and toluene (TO), which provides an additional variable for the identification of different analytes in the same category.