Metal clusters exhibit diverse structures, emerging functions, and applications; thus, incorporating clusters into metal-organic frameworks (MOFs) brings tremendous merits. Although the construction of cluster-based MOFs is sophisticated, the reticular materials constructed from a combination of the chemistry of metal clusters and covalent organic frameworks (COFs) remain unexplored. Herein, we prepared two Cu(I) cluster-based MOFs with cyclic trinuclear units (CTUs), termed JNM-1 and JNM-2, either by a stepwise synthetic approach or by a one-pot reaction, for networking clusters with dynamic covalent chemistry, rarely utilized in MOF synthesis. The generated JNMs exhibited excellent stability and could be used as recyclable catalysts for palladium-free Sonogashira coupling reactions with high efficiency and tolerance (>90% yield for nine examples), without loss of performance for at least five cycle runs. In addition, conjugated single molecular wires with lengths ranging from 1.6 to 2.7 nm were synthesized feasibly using the JNM-1 catalyst.
Adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of distillation separation of propylene/propane; however, very challenging to realize.A new flexible MOF material [Zn 2 (BDC-Cl) 2 (Py 2 TTz)] with doubly interpenetrated pillared paddle wheel structure of pcu (primitive cubic) topology has been realized for this difficult separation for the first time. Through judicious choice of linkers, the framework has small pore apertures that takes up much more propylene adsorption than propane. The selective adsorption relies on the sieving effect of the flexible framework. Column breakthrough experiment further demonstrated that the efficient separation can be achieved under dynamic conditions.
Phosphorescent organic light emitting diodes (PhOLEDs) are required to reach sufficiently high devices’ performance, however, synthesis of the phosphorescent emitter with high quantum efficiency and short lifetime remains great a...
Coordination complexes with aggregation-induced-emission (AIE) behavior has drawn much attention because of their promising applications. Conventionally, the AIE-active metal–organic complexes are prepared from an AIE-active organic ligand, and the construction of such coordination complexes from aggregation-caused-quenching (ACQ) ligands is still challenging. Herein, we have synthesized two new cyclic trinuclear complexes (CTCs), namely, 1 and 2, from copper(I) and silver(I) and a ACQ ligand [4-(3,5-dimethyl-1H-pyrazol-4-yl)benzaldehyde, HL]. (1) exhibited AIE behavior, and the emission intensity is enhanced ∼20 times when it aggregates, which can be attributed to its tight packing and multiple intermolecular hydrogen bonds that restrained the intramolecular rotation, as confirmed by single-crystal X-ray diffraction analysis. On the other hand, (2) displayed ACQ effects, and the emission intensity is decreased ∼5 times when it aggregates. This ACQ behavior of 2 is related to its loose packing and free rotation of the ligand in crystals, resulting in nonradiative decay and fluorescence quenching. Interestingly, the CTCs 1 and 2 both exhibited a good affinity to gold(III) ions, allowing selective detection and sensing of gold ions. More importantly, the 2 shows a good limit of detection (3.28 μmol/L) and an ultrafast responsive time (∼2 s). Our studies pave a new route to designing novel AIE-active coordination complexes and further exploring the functionality of CTCs.
Metal-organic polyhedras (MOPs, also known as metal-organic cages or supramolecular coordination cages), are discrete assemblies composed from metal ions and organic linkers. [1][2][3][4][5][6][7][8][9][10] Due to their intriguing structures [1][2][3][4][5][6][7] as well as potential applications in molecular recognition, [3,4] adsorption and separation, [7,11,12] catalysis, [9][10][11]13] sensing, [14] and photoluminescence, [15] MOPs have attracted considerable attentions. Utilizing the metaldirected self-assembly strategy, the single metal-based MOPs with various architectures have been sophistically synthesized by Fujita, [3][4][5] Stang, [6,7] Raymond, [8,9] Nitschke, [10,11] and others groups. [12,[14][15][16][17][18] Recently, Yaghi and O'Keeffe introduced the concept of reticular [19] chemistry into MOPs, which allows chemists to rationally design MOPs with certain geometry by combing polynuclear metal-cluster nodes as secondary building units (SBUs) and organic linkers. [20] Due to the multiple coordination sites and high stability, the introduction of metal clusters into MOPs can not only improve their stability, but also enrich their structural complexity and functionality. [21][22][23][24] So far, although tremendous SBUs have been used in the metal-organic frameworks (MOFs), only few SBUs, mostly metal carboxylate clusters and metal oxide clusters, [21][22][23][24] were employed in the preparation of discrete MOPs, limiting the chemical diversity of metal cluster-based MOPs.Copper(I) iodide (CuI) is able to form diverse aggregates or clusters [Cu m I n ] with potential applications as luminescent and catalytic materials. [25] A wealth of coordination complexes and MOF structures containing [Cu m I n ] clusters were discovered with advanced functions. It is envisioned that [Cu m I n ] clusterbased MOPs would exhibit unusual structures with interesting luminescent and catalytic properties. However, subtle changes of synthetic conditions (e.g., solvent, temperature, or organic linkers) led to significant impact on the structures of [Cu m I n ] clusters, resulting in the difficulty in precise control of their structures and coordination modes. [26][27][28][29][30][31][32] To our best knowledge, self-assembly of [Cu m I n ] cluster-based MOPs has never been reported and still remains highly challenging.Conventionally, click chemistry is a thermal process catalyzed by Cu(I). Photocatalyzed click reactions have aroused recent research interests due to their mild reaction conditions and
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