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

/pdf/metal-organic-frameworks-and-self-assembled-supramolecular-2xs948xxr9.pdf

Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

The literature on open-framework materials has shown numerous examples of porous solids with additional structural, chemical, or physical properties. These materials show promise for applications ranging from sensing, catalysis and separation to multifunctional materials. This critical review provides an up-to-date survey to this new generation of multifunctional open-framework solids. For this, a detailed revision of the different examples so far reported will be presented, classified into five different sections: magnetic, chiral, conducting, optical, and labile open-frameworks for sensing applications. (413 references.)

Old materials with new tricks: multifunctional open-framework materials.

2.4.2. Interpenetrated Ladders 711 2.4.3. Unusual Motifs of Ladders 713 2.4.4. Properties of Ladderlike Chains 713 2.5. Rotaxane Polymers 714 2.5.1. 1D Polyrotaxanes 714 2.5.2. 2D Polyrotaxanes 715 2.5.3. 3D Polyrotaxanes 716 2.5.4. Hydrogen-Bonded Polyrotaxanes 716 2.6. Ribbon/Tape Polymers 717 2.7. Metal Cluster As Building Blocks for 1D CP 718 2.7.1. Metal Carboxylate Clusters 718 2.7.2. Metal Halide Clusters 719 2.7.3. Metal Chalcogenide Clusters 720 2.7.4. Polyoxometalate Clusters 721 2.7.5. Single Molecular Magnets as Building Blocks 722

One-Dimensional Coordination Polymers: Complexity and Diversity in Structures, Properties, and Applications

Three novel interesting coordination polymers, [Cd3(SIP)2(bbi)5·3H2O]n (1), [Co3(SIP)2(bix)4(2H2O)·2H2O]n (2), and [Cd(2,5-pydc)2(bix)1.5·H2O]n (3) (SIP = 5-sulfoisophthalic acid monosodium salt; bbi = 1,1‘-(1,4-butanediyl)bis(imidazole); bix = 1,4-bis(imidazol-1-ylmethyl)-benzene; 2,5-pydc = pyridine-2,5-dicarboxylic acid), have been isolated under hydrothermal conditions and structurally characterized. Polymer 1 has a 3D complicated framework comprised of an infinite 1D ladder-like chain and 2D layer structure. Polymer 2 features a 3D hydrated framework with uncoordinated water molecules trapped in the pores. Polymer 3 is a 2D infinite layer framework, which is further interconnected by hydrogen-bond interactions to lead to a 3D supramolecular architecture. Compounds 1 and 3 exhibit medium-strong fluorescent emissions in the solid state at room temperature and could be significant in the field of photoactive materials.

Syntheses, Structures, and Physical Properties of Three Novel Metal−Organic Frameworks Constructed from Aromatic Polycarboxylate Acids and Flexible Imidazole-Based Synthons

Five novel interesting d10 metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4‘-bpy)2(H2O)2·3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi)·0.5H2O]n (bbi = 1,1‘-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)1.5·1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 41 helices running along the c-axis with a pitch of 10.090 A. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, ...

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

An interesting magnetic behavior in molecular solid containing one-dimensional Ni(III) chain

Two new metal−organic frameworks (MOFs), [Zn(p-BDC)(m-bix)0.5][Zn(p-BDC)(m-bix)]·H2O (1) and [Zn(p-BDC)(m-bix)] (2) (p-BDC = terephthalate, m-bix =1,3-bis(imidazol-1-ylmethyl)benzene), were synthesized and characterized structurally. Both of the MOFs feature the interpenetrated two-dimensional (2D) → three-dimensional (3D) network motifs. In particular, complex 1 represents the second example of intertwining of different 2D coordination motifs, and complex 2 shows a 3-fold parallel interpenetrated framework. In addition, the spectroscopic, thermal, and fluorescence properties of complexes 1 and 2 are investigated.

Flexible ligand, structural, and topological diversity : Isomerism in Zn(NO3)2 coordination polymers

Synthesis, crystal structure and magnetic property of a new 1D molecular material [1-(4′-chlorobenzyl)–4-aminopyridinium](+) bis(maleonitriledithiolato)nickel(–)

Zhengfang Tian

Papers

Syntheses, Structures, and Physical Properties of Three Novel Metal−Organic Frameworks Constructed from Aromatic Polycarboxylate Acids and Flexible Imidazole-Based Synthons

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

An interesting magnetic behavior in molecular solid containing one-dimensional Ni(III) chain

Flexible ligand, structural, and topological diversity : Isomerism in Zn(NO3)2 coordination polymers

Synthesis, crystal structure and magnetic property of a new 1D molecular material [1-(4′-chlorobenzyl)–4-aminopyridinium](+) bis(maleonitriledithiolato)nickel(–)