Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

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

Lanthanide-based luminescent hybrid materials.

Metal–organic frameworks based on trivalent lanthanides (LnMOFs) are a very promising class of materials for addressing the challenges in engineering of luminescent centres. Lanthanide-bearing phosphors find numerous applications in lighting, optical communications, photonics and biomedical devices. In this critical review we discuss the potential of LnMOFs as multifunctional systems, which combine light emission with properties such as microporosity, magnetism, chirality, molecule and ion sensing, catalysis and activity as multimodal imaging contrast agents. We argue that these materials present a unique chance of observing synergy between several of these properties, such as the coupling between photoluminescence and magnetism. Moreover, an integrated approach towards the design of efficient, stable, cheap, environmentally-friendly and multifunctional luminescent LnMOFs is still missing. Although research into LnMOFs is at its early stage and much basic knowledge is still needed, the field is ripe for new ideas, which will enable sensor devices and photonic prototypes to become a commercial reality (81 references).

Luminescent multifunctional lanthanides-based metal–organic frameworks

Terminal ligand effect on the structure variation of Copper(II) complexes

Two novel copper(II) complexes, [Cu4(tacn)2(Hdmg)2(dmg)2](ClO4)2 (1) and [Cu2(dmg)(Hdmg)(H2dmg)(H2O)]ClO4 (2), bridged by dimethylglyoxime have been synthesized and characterized by single crystal X-ray diffraction method.

Binuclear and Tetranuclear Copper(II) Complexes Bridged by Dimethylglyoxime

A fluorescent probe for Zn ions has the chemical formula: [Ln(PDA)3Mn1.5(H2O)3].3.25 H2O, where Ln is Eu or Lu and PDA is 2.6-pyridinedioic acid ligand. Two coordinate polymers Eu-Mn and Tb-Mn, which has 3D nano-artery structure, are synthesized. The intensity of their fluorescent peak is increased when the concentration of Zn ions in N,N'-dimethyl methylamide solvent is increased.

Rare earth transition mixed metal compounding material type zine ion fluorescent probe and its preparation method

Three 3, 5-dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)4(H2O)](ClO4)2 (1), [Cu(pz*)2(NCS)2]·H2O (2), and [Cu(pz*)2(OOCCH=CHCOO)(H2O)]·1.5H2O (3), have been synthesized and characterized with single crystal X-ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) A, c = 16.301 (5) A, and Z = 4. 2 crystallizes in the monoclinic space group, P21/c, with a = 8.008 (3) A, b = 27.139 (9) A, c = 8.934 (3) A, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) A, b = 10.891 (13) A, c = 11.822 (14) A, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1, one water molecule and four pz* ligands are coordinated to CuII. Two [Cu(pz*)4(H2O)]2+ units are connected to ClO4— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2, which forms an one-dimensional chain via intermolecular hydrogen bonds with the N-H atom of pz*. In 3, the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N-H atom of pz* to create a two-dimensional structure. The spectroscopic and bond properties are also discussed.



Kupfer(II)-Koordinationsverbindungen mit 3, 5-Dimethylpyrazol — Synthese, Kristallstruktur und Eigenschaften



Drei 3, 5-Dimethylpyrazol-Kupfer(II)-Komplexe, [Cu(pz*)4(H2O)](ClO4)2 (1), [Cu(pz*)2(NCS)2]·H2O (2) und [Cu(pz*)2(OOCCH=CHCOO)(H2O)]·1.5H2O (3) (pz* = 3, 5-Dimethylpyrazol) wurden synthetisiert und durch Einkristallstrukturanalysen charakterisiert. 1 kristallisiert in der tetragonalen Raumgruppe, 14/m, mit a = 14.027 (3) A, c = 16.301 (5) A und Z = 4. 2 kristallisiert in der monoklinen Raumgruppe, P21/c, mit a = 8.008 (3) A, b = 27.139 (9) A, c = 8.934 (3) A, β = 106.345 (6)° und Z = 4. 3 kristallisiert in der triklinen Raumgruppe, P1, mit a = 7.291 (9) A, b = 10.891 (13) A, c = 11.822 (14) A, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60° und Z = 2. In 1 sind ein Wassermolekul und vier pz*-Liganden an CuII koordiniert. Zwei [Cu(pz*)4(H2O)]2+-Einheiten sind an ClO4— durch Wasserstoffbruckenbindungen gebunden. Ein Wassermolekul wird in der Elementarzelle von 2 gefunden. 2 bildet eine Kette durch intermolekulare Wasserstoffbruckenbindungen mit dem N—H-Atom von pz*. In 3 ist das Sauerstoffatom des koordinierten Wassermolekuls mit zwei C=O-Gruppen der zwei benachbarten Maleinsaure-Molekulen verbunden und bildet eine lineare parallelogrammartige Struktur. Eine weitere C=O-Gruppe der Maleinsaure bildet uber eine Wasserstoffbruckenbindung mit dem N—H-Atom von pz* eine zweidimensionale Struktur. Die spektroskopischen- und Bindungseigenschaften werden ebenfalls diskutiert.

Xiao-Yan Chen

Papers

Terminal ligand effect on the structure variation of Copper(II) complexes

Binuclear and Tetranuclear Copper(II) Complexes Bridged by Dimethylglyoxime

Rare earth transition mixed metal compounding material type zine ion fluorescent probe and its preparation method

Molecular and Low-dimensional Coordination Compounds of Copper(II) and 3, 5-Dimethylpyrazole — Synthesis, Crystal Structure, and Properties

A novel coordination polymer with dicyanamide ligand: multi-dimensional architecture stabilized by hydrogen bonding