This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)

Hybrid porous solids: past, present, future

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

A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI3, where A is the methylammonium (CH3NH3+) or formamidinium (HC(NH2)2+) cation and M is Sn (1 and 2) or Pb (3 and 4) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of 1–4 classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a ...

Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties.

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

Three novel complexes, Cd3tma2·13H2O (1), Cd3tma2·dabco·2H2O (2), and Cd3Htma3·8H2O (3) (tma = trimesate), of cadmium(II)−trimesate coordination polymers are obtained from hydrothermal reaction. 1 ...

Synthesis, structure, and fluorescence of the novel cadmium(II)-trimesate coordination polymers with different coordination architectures.

Structural overview and structure–property relationships of iodoplumbate and iodobismuthate

The combination of lone-pair effects on Pb2+ cations and the smaller electronegativity of I− anions into the pentaborate framework generates a phase-matchable material, Pb2B5O9I, with the largest powder SHG response among borates, about 13.5 times that of KDP (KH2PO4), and transparency over the near-UV to middle-IR region. DFT calculations on electronic structure and cutoff-energy-dependent SHG coefficients confirm these origins.

Pb2B5O9I: an iodide borate with strong second harmonic generation.

The unique porous metal−organic framework {KCo3(C6H4O7)(C6H5O7)(H2O)2·8H2O}8 (1), which exhibits an unprecedented infinite 3D (3,6)-connected decorated anatase net, has been obtained by hydrothermal reaction. Upon dehydration, the compound retains crystallinity and exhibits a type I N2 sorption isotherm, characteristic of a microporous solid with apparent Langmuir surface area 939 m2/g and pore volume 0.31 cm3/g. Magnetic measurements for both 1 and dehydrated 1 show the spin-canted antiferromagnetic state below 5 K and a magnetic hysteresis loop at 2 K. Thus, dehydrated 1 represents the first metal−organic framework for which microporosity and a spin-canted antiferromagnetic state coexist, which demonstrates that the self-assembly of organo-polymetal clusters and metal ions can provide a potential route to magnetic porous metal−organic frameworks.

Xintao Wu

Papers

Synthesis, structure, and fluorescence of the novel cadmium(II)-trimesate coordination polymers with different coordination architectures.

Structural overview and structure–property relationships of iodoplumbate and iodobismuthate

Pb2B5O9I: an iodide borate with strong second harmonic generation.

A 3D canted antiferromagnetic porous metal-organic framework with anatase topology through assembly of an analogue of polyoxometalate

Semisacrificial Template Growth of Self-Supporting MOF Nanocomposite Electrode for Efficient Electrocatalytic Water Oxidation