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

Luminescent metal–organic frameworks for chemical sensing and explosive detection

Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure–property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

Luminescent sensors based on metal-organic frameworks

Metal-organic frameworks (MOFs) as chemical sensors have developed rapidly in recent years. There have been many papers concerning this field and interest is still growing. The reason is that the specific merits of MOFs can be utilized to enhance sensitivity and selectivity by various energy/charge transfers occurring among different ligands, ligand, and metal centers, such as from ligands to metal centers or metal centers to ligands, as well as from MOF skeletons to guest species. This review intends to provide an update on recent progress in various applications of different MOF-based sensors on the basis of their luminescent and electrochemical responses towards small molecules, gas molecules, ions (cations and anions), pH, humidity, temperature, and biomolecules. MOF-based sensors function by utilizing different mechanisms, including luminescent responses of "turn-on" and "turn-off", as well as electrochemical responses.

Chemical Sensors Based on Metal–Organic Frameworks

Metal-organic frameworks (MOFs) with multiple emission centers are newly emerging as ratiometric sensors owing to their high sensitivity and high selectivity toward a wide range of targeted functional species. Energy transfer between the light-absorbing group and emission centers and between different emission centers is the key to rationally design and synthesize MOF-based ratiometric sensors. A good match between the energy levels of the light-absorbing groups and emission centers is the prerequisite for MOF-based sensors to exhibit multiple emissions, and a good match of the MOF-based sensors and those of the targeted species can increase the sensitivity and selectivity, but this match is highly challenging to obtain via synthesis. MOFs with multiple emission centers can be produced by functionalizing MOFs with multiple lanthanide centers, organic luminophores, dyes, carbon dots, and other such emissive groups. In this progress report, recent advances in the strategies for synthesizing MOFs with multiple emission centers and their applications for ratiometric sensing of solution conditions, including the pH value, and ion, organic molecule, and biomolecule concentrations, are summarized, as are the related sensing mechanisms.

Multicenter Metal-Organic Framework-Based Ratiometric Fluorescent Sensors.

A new bimetallic lanthanide metal-organic framework [Eu0.5 Tb1.5 (FDA)3 ] (H2 FDA = 2,5-furandicarboxylic acid) exhibits high-sensitivity luminescent sensing of mixtures of organic compounds and can work over a large range of volume ratios. The self-calibrating behavior of this color-gradient luminescent sensor is presented for the first time.

A Bimetallic Lanthanide Metal-Organic Material as a Self-Calibrating Color-Gradient Luminescent Sensor.

Two new isostructural 3D lanthanide metal–organic frameworks (Ln-MOFs) {[Ln4(μ3-OH)4(BPDC)3(BPDCA)0.5(H2O)6]ClO4·5H2O}n (Ln = Tb (1) and Gd (2), BPDC2– = 3,3′-dicarboxylate-2,2′-dipyridine anion and BPDCA2– = biphenyl-4,4′-dicarboxylate anion) based on cubane-shaped [Ln4(μ3-OH)4]8+ clusters were successfully synthesized and fully characterized. There are two kinds of micropores with dimensions of 3.0 × 7.0 A2 along the b-axis and 4.5 × 5.5 A2 along the c-axis in the cationic framework. Ln-MOF 1 exhibits an intensive green luminescence triggered by the efficient antenna effect of ligands under UV light. Luminescent studies illustrate that Ln-MOF 1 could be an efficient multifunctional luminescent material for high-sensitivity sensing of small organic molecules, metal cations, and anions, especially for benzene and acetone, Cu2+, and CrO42–. The mechanism of the sensing properties was studied in detail as well. Additionally, this cationic framework also displays fast capture of pollutant CrO42– by anion exc...

Experimental Studies and Mechanism Analysis of High-Sensitivity Luminescent Sensing of Pollutional Small Molecules and Ions in Ln4O4 Cluster Based Microporous Metal–Organic Frameworks

A rare, robust microporous lanthanide metal-organic framework with 1D honeycomb-type channels is presented. Excellent adsorption capabilities for N(2), H(2), and CO(2) and significant selective sorption of CO(2) over N(2) and CH(4) were observed. Moreover, the guest-dependent luminescent behavior of these lanthanide materials shows a potential use for the sensing of small-molecule pollutants such as benzene and acetone.

Highly selective sorption and luminescent sensing of small molecules demonstrated in a multifunctional lanthanide microporous metal-organic framework containing 1D honeycomb-type channels.

A ligand design approach, which requires rational design of ligand based on the knowledge of specific target, was applied for the synthesis of two interesting and robust MOFs 1 and 2 containing unusual several types of copper(II) secondary building units (SBUs). Thanks to unsaturated metal centers (UMCs) and azo group, microporous material 1 exhibited not only high CO2 uptake but also an impressive selective adsorption of CO2 over CH4 and N2. Moreover, a high H2 uptake of 1 was also observed.

Dual-functionalized metal-organic frameworks constructed from hexatopic ligand for selective CO2 adsorption.

Four new metal–organic frameworks (MOFs), {[Co2(L)2(DMF)3]·6.5DMF·5H2O}n (1), {[Cu(L)(H2O)]·2DMA}n (2), {[Zn2(L)(DMF)2(HCOO)2]·3DMF·2H2O}n (3), and {[Cd2(L)2(DMF)(H2O)(μ2-OH2)2]·3.5DMF·2H2O}n (4) (H2L = N-phenyl-N′-phenylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide dicarboxylic acid; DMA = N,N-dimethylacetamide; DMF = N,N-dimethylformamide) have been synthesized under solvothermal conditions. MOFs 1, 2 and 3 display various interesting two-dimensional (2D) structures, including 2D lattice structure, 2-fold interpenetrated 2D structure, and 2D tube-based network. MOF 4 features an interesting two-fold interpenetrated 3D structure possessing a 6-connected pcu network with the point symbol of {412·63}. Photoluminescent properties of MOFs 3 and 4 have been investigated in the solid state at room temperature.

Structural diversity of four new metal–organic frameworks with a curved tetracarboxdiimide dicarboxylic acid

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