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

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.

The field of inorganic open-framework materials is dominated by aluminosilicates and phosphates. The metal carboxylates have emerged as an important family in the last few years. This family includes not only mono- and dicarboxylates of transition, rare-earth, and main-group metals, but also a variety of hybrid structures. Some of the carboxylates possess novel adsorption and magnetic properties. Dicarboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties. In some of these structures, the dicarboxylate acts as a linker between two inorganic units. Hybrid nanocomposites are also of particular note, for example, cadmium oxalate host lattices that can accommodate extended alkali-metal halide structures. This Review discusses the synthesis, structure, and properties of various types of open-framework metal carboxylates.

Metal carboxylates with open architectures.

Luminescent sensors based on metal-organic frameworks

The solvothermal reaction of zinc acetate dihydrate with a mixture of benzene-1,4-dicarboxylic acid (H(2)BDC) and benzene-1,3,5-tricarboxylic acid (H(3)BTC) in a solution containing N,N'-dimethylformamide (DMF), absolute ethanol, and chlorobenzene gave rise to a metal-organic polymer, Zn(3).BDC.2BTC.2NH(CH(3))(2).2NH(2)(CH(3))(2). The structure of this polymer possesses a unique three-dimensional framework with tri-zinc clusters, and BDC and BTC units colinking the clusters. Moreover, this metal-organic polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 430 nm (lambda(ex) = 325 nm). Crystal data for this compound (C(17)H(20)N(2)O(8)Zn(1.5)): monoclinic, space group P2(1)/n, cell dimensions a = 11.6171(3) A, b = 14.2456(4) A, c = 12.6426(3) A, beta = 107.030(2) degrees, V = 2000.51(9) A(3), and Z = 4.

Photoluminescent metal-organic polymer constructed from trimetallic clusters and mixed carboxylates.

A unique metal–organic polymer Mn·PDB·H2O (H2PDB = pyridine-3,4-dicarboxylic acid), with weak antiferromagnetic interactions both between the manganese(II) centers of an infinite Mn–O–C chain and between the adjacent chains, has been synthesized by the hydrothermal reaction of Mn(CH3COO)2·4H2O with H2PDB; X-ray diffraction shows that the polymer possesses a one-dimensional rectangular channel built up from pyridine rings and pseudo-layers formed by infinite straight Mn–O–C chain building units.

Assembly of a manganese(II) pyridine-3,4-dicarboxylate polymeric network based on infinite Mn–O–C chains

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Photoluminescent metal-organic polymer constructed from trimetallic clusters and mixed carboxylates.

Assembly of a manganese(II) pyridine-3,4-dicarboxylate polymeric network based on infinite Mn–O–C chains