Luminescent Functional Metal–Organic Frameworks

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

The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

/pdf/engineering-coordination-polymers-towards-applications-3joywh2v74.pdf

Engineering coordination polymers towards applications

This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

/pdf/secondary-building-units-nets-and-bonding-in-the-chemistry-o0m4ttzsgz.pdf

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design

The general large-scale synthesis of a family of single-crystalline transition metal tungstate nanorods/nanowires is easily realized by a hydrothermal crystallization technique under mild conditions using cheap and simple inorganic salts as precursors. Uniform tungstate nanorods/nanowires such as MWO4 (M = Zn, Mn, Fe), Bi2WO6, Ag2WO4, and Ag2W2O7 with diameters of 20–40 nm, lengths of up to micrometers, and controlled aspect ratios can be readily obtained by hydrothermal transformation and recrystallization of amorphous particulates. This novel and efficient pathway toward various kinds of related low-dimensional tungstate nanocrystals under mild conditions could open new opportunities for further investigating the novel properties of tungstate materials.

General Synthesis of Single-Crystal Tungstate Nanorods/Nanowires: A Facile, Low-Temperature Solution Approach

Photochromism of a Methyl Viologen Bismuth(III) Chloride: Structural Variation Before and After UV Irradiation

A series of homodinuclear lanthanide(III) complexes with the 4-cba ligand, [La2(4-cba)6(phen)2(H2O)6] (1) and [Ln2(4-cba)6(phen)2(H2O)2] (Ln = Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), and Dy (7); 4-Hcba = 4-cyanobenzoic acid; phen = 1,10-phenanthroline), have been synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, two water molecules bridge two nine-coordinated La ions, and six 4-cba ligands coordinate to the two La ions in terminal mode. In the isostructural complexes 2−7, two eight-coordinated Ln ions are connected by four bidentate 4-cba ligands, and another two 4-cba ligands terminate the two Ln ions. The variable-temperature magnetic properties of 2−7 have been investigated. Complex 7 shows a significant ferromagnetic interaction between Dy(III), while no magnetic interaction exists between Gd(III) ions in 6. In 2−5, the value of χMT decreases with decreasing temperature, but the magnetic interactions between the Ln(III) ions cannot definitely be concluded. Notably, ...

Crystal structures and magnetic and luminescent properties of a series of homodinuclear lanthanide complexes with 4-cyanobenzoic ligand.

A white-light-emitting borate-based inorganic-organic hybrid open framework

The one-dimensional polymer, [Cu2(C8H6N2)2(C7H6N2)]2[Mo8O26] (1), which consists of β-[Mo8O26]4- anions linked by quinoxaline and its oxidized product benzimidazole ligands coordinated to binuclear copper(I) fragments, provides the first demonstration that the isolated copper(I) complex under hydrothermal conditions “captures” the reduction product of original starting organonitrogen ligand to form a copper(I)−β-octamolybdate complex.

Hybrid coordination polymer constructed from β-octamolybdates linked by quinoxaline and its oxidized product benzimidazole coordinated to binuclear copper(I) fragments

Jin-Shun Huang

Papers

General Synthesis of Single-Crystal Tungstate Nanorods/Nanowires: A Facile, Low-Temperature Solution Approach

Photochromism of a Methyl Viologen Bismuth(III) Chloride: Structural Variation Before and After UV Irradiation

Crystal structures and magnetic and luminescent properties of a series of homodinuclear lanthanide complexes with 4-cyanobenzoic ligand.

A white-light-emitting borate-based inorganic-organic hybrid open framework

Hybrid coordination polymer constructed from β-octamolybdates linked by quinoxaline and its oxidized product benzimidazole coordinated to binuclear copper(I) fragments