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).

In this work we demonstrate the concept of stress-induced chemical detection using metalorganic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be efficiently converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N 2 or O 2 . The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO 2 . We also report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. A force field model is described that successfully predicts changes in MOF properties and the uptake of gases. This model is used to predict adsorption isotherms for a number of representative compounds, including explosives, nerve agents, volatile organic compounds, and polyaromatic hydrocarbons. The results show that, as a result of relatively large heats of adsorption (> 20 kcal mol -1 ) in most cases, we expect an onset of adsorption by MOF as low as 10 -6 kPa, suggesting the potential to detect compounds such as RDX at levels as low as 10 ppb at atmospheric pressure.

Synthetic methods used to produce metal nanoparticles typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal-organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with the potential for both steric and chemical stabilization. We report a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions < or =1 nm, with a significant fraction existing as Ag(3) clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible.

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A colorimetric chemodosimeter (SQ1) for the detection of trace palladium salts in cross-coupling reactions mediated by palladium is described. Decolorization of SQ1 is affected by nucleophilic attack of ethanethiol in basic DMSO solutions. Thiol addition is determined to have an equilibrium constant (K(eq)) of 2.9 × 10(6) M(-1), with a large entropic and modest enthalpic driving force. This unusual result is attributed to solvent effects arising from a strong coordinative interaction between DMSO and the parent squaraine. Palladium detection is achieved through thiol scavenging from the SQ1-ethanethiol complex leading to a color "turn-on" of the parent squaraine. It was found that untreated samples obtained directly from Suzuki couplings showed no response to the assay. However, treatment of the samples with aqueous nitric acid generates a uniform Pd(NO(3))(2) species, which gives an appropriate response. "Naked-eye" detection of Pd(NO(3))(2) was estimated to be as low as 0.5 ppm in solution, and instrument-based detection was tested as low as 100 ppb. The average error over the working range of the assay was determined to be 7%.

[reaction: see text] The dependence of acidity on Li+ coordination geometry to alpha-carbon acids is investigated by generating potential energy surfaces of Li+ complexation with acetaldehyde and its respective enolate. The global minimum for the enolate complex shows significant Li+-pi-system coordination to both oxygen and the alpha-carbon. The gas-phase acidity analysis reveals significantly more alpha-carbon coordination, which presumably enhances the lability of the cleaving proton in the transition state of deprotonation.

We demonstrate a versatile, bottom-up method of forming metal and semiconducting nanoparticles by exposing precursor metal-organic frameworks (MOFs) to an electron beam. Using a transmission electron microscope to initiate and observe growth, we show that the composition, size, and morphology of the nanoparticles are determined by the chemistry and structure of the MOF, as well as the electron beam properties. Zinc oxide, metallic indium and copper particles were produced with narrow and tunable size distributions comparable to those obtained from state-of-the-art methods. This method represents a first step toward the fabrication of nanoscale heterostructures using the highly controlled environment of the MOF pores as a scaffold or template.