Ze Chang

A luminescent metal–organic framework demonstrating ideal detection ability for nitroaromatic explosives

A 3D metal–organic framework, [NH2(CH3)2]2[Cd17(L)12(μ3-H2O)4(DMF)2(H2O)2]·solvent (1), has been constructed with a π-electron rich aromatic ligand 2,4,6-tris[1-(3-carboxylphenoxy)ylmethyl]mesitylene (H3L) and d10 configuration metal ion Cd2+ under solvothermal conditions. The crystal structure reveals that complex 1 consists of hexanuclear and trinuclear cadmium building units, which are further bridged by the multicarboxylate ligands to give a (3, 6, 12)-connected topological net. This complex exhibits strong ligand originated photoluminescence emission, which is selectively sensitive to electron-deficient nitroaromatic explosives (nitrobenzene, 4-nitrotoluene, 1,4-dinitrobenzene, 1,3-dinitrobenzene and 2,4-dinitrotoluene). This property makes complex 1 a potential fluorescence sensor for these chemicals.

A Controllable Gate Effect in Cobalt(II) Organic Frameworks by Reversible Structure Transformations

With H2 O or NH3 stimuli, the blue cobalt-based metal-organic framework (MOF) BP can reversibly transform to red RP. The removal/recovery of terephthalate ligands accompanied by the transformation leads to a gate effect, which allows the encapsulation and release of small solvent molecules under certain conditions. This is the first example of topology transformation from a self-penetrating to interpenetrating net in 3D MOFs.

A luminescent 2D coordination polymer for selective sensing of nitrobenzene

A luminescent two-dimensional (2D) coordination polymer is demonstrated to be a selective sensing material for the straightforward detection of nitrobenzene via a redox fluorescence quenching mechanism.

A Cu(I) metal–organic framework with 4-fold helical channels for sensing anions

A new Cu(I) metal–organic framework, {[Cu(pytpy)]·NO3·CH3OH}∞ (1), which is a 4-fold interpenetrating 3D framework with (10,3)-b topology, has been synthesized by self-assembly of Cu(NO3)2·3H2O with 2,4,6-tris(4-pyridyl)pyridine (pytpy) in mixed-solvent. The guest methanol molecules in the channels of 1 could be replaced by water molecules via a single-crystal-to-single-crystal (SC–SC) process, and the hydrated complex could serve as a host for sensing anions with different geometries which can be conveniently recognized visually. Moreover, the desolvated complex shows selective uptake of CO2 over N2 at ambient temperature.

Two luminescent metal–organic frameworks for the sensing of nitroaromatic explosives and DNA strands

With a flexible aromatic ligand, bis-(3,5-dicarboxy-phenyl)terephthalamide (H4L), two metal–organic frameworks, Cd(L)·(HDMA)2(DMF)(H2O)3 (1) and Zn(L)·(HDMA)2(DMF)(H2O)6 (2), were synthesized using a solvothermal method. Both 1 and 2 possess a 3D open framework. These two compounds exhibit strong photoluminescence in suspensions, and their luminescence could be efficiently and selectively quenched by a series of nitroaromatics. Thus, 1 and 2 could be used as excellent luminescent probes for nitroaromatic explosives. Additionally, 1 and 2 could also be utilized as the sensing platforms for DNA strands, which is attributed to their different affinities for single- and double-stranded DNAs. With this method, 0.05 nM of target DNA could be detected, and the selectivity could be down to a single nucleotide mismatch. This work shows the potential of MOFs for the sensing of versatile chemicals.

A Mixed Molecular Building Block Strategy for the Design of Nested Polyhedron Metal–Organic Frameworks

A mixed molecular building block (MBB) strategy for the synthesis of double-walled cage-based porous metal-organic frameworks (MOFs) is presented. By means of this method, two isostructural porous MOFs built from unprecedented double-walled metal-organic octahedron were obtained by introducing two size-matching C3 -symmetric molecular building blocks with different rigidities. With their unique framework structures, these MOFs provide, to the best of our knowledge, the first examples of double-walled octahedron-based MOFs.

Flexible Metal–Organic Frameworks: Recent Advances and Potential Applications

Flexible metal-organic frameworks (MOFs) receive much attention owing to their attractive properties that originate from their flexibility and dynamic behavior, and show great potential applications in many fields. Here, recent progress in the discovery, understanding, and property investigations of flexible MOFs are reviewed, and the examples of their potential applications in storage and separation, sensing, and guest capture and release are presented to highlight the developing trends in flexible MOFs.

New Three-Dimensional Porous Metal Organic Framework with Tetrazole Functionalized Aromatic Carboxylic Acid: Synthesis, Structure, and Gas Adsorption Properties

5-(1H-Tetrazol-1-yl)isophthalic acid (H(2)L) reacts with Cu(II) ion forming a new metal-organic framework {[CuL]·DMF·H(2)O}(∞) (1) (DMF = N,N-dimethylformamide), with a rutile-related type net topology. Compound 1 possesses a 3D structure with 1D channels that can be desolvated to yield a microporous material. Adsorption properties (N(2), H(2), O(2), CO(2), and CH(4)) of the desolvated solid [CuL] (1a) have been studied, and the results exhibit that 1a possesses fairly good capability of gas sorption for N(2), H(2), O(2), and CO(2) gases, with high selectivity ratios for O(2) over H(2) at 77 K and CO(2) over CH(4) at 195, 273, and 298 K. Furthermore, 1a has excellent O(2) uptake at 77 K and a remarkably high quantity of adsorption for CO(2) at room temperature (298 K) and atmospheric pressure, suggesting its potential applications in gas separation or purification.

Crystalline Capsules: Metal-Organic Frameworks Locked by Size- Matching Ligand Bolts**

Metal-organic frameworks (MOFs) are shown to be good examples of a new class of crystalline porous materials for guest encapsulation. Since the encapsulation/release of guest molecules in MOF hosts is a reversible process in nature, how to prevent the leaching of guests from the open pores with minimal and nondestructive modifications of the structure is a critical issue. To address this issue, we herein propose a novel strategy of encapsulating guests by introducing size-matching organic ligands as bolts to lock the pores of the MOFs through deliberately anchoring onto the open metal sites in the pores. Our proposed strategy provides a mechanical way to prevent the leaching of guests and thereby has less dependence on the specific chemical environment of the hosts, thus making it applicable for a wide variety of existing MOFs once the size-matching ligands are employed.

Fluorous Metal-Organic Frameworks with Enhanced Stability and High H2/CO2 Storage Capacities

A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation.