A Copper Iodide Cluster‐Based Metal–Organic Polyhedra for Photocatalytic Click Chemistry

Abstract

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

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

“…These results are indicative of the radical nature of the Cu 57 -catalyzed click reaction (Scheme S2). [13] Notably, the reaction does not proceed in the absence of copper nanoclusters or other catalysts (entry 7). To clarify the catalytic differences between Cu 57 and Cu 58 , a time-dependent kinetic study of photoinduced AAC was performed.…”

Bridging and Fixing Metal–Organic Cages

“…Over the past two decades, metal–organic cages (MOCs) composed of metal clusters and organic linkers have attracted significant research attention owing to their well-defined structures, intrinsic porosities, and solution processabilities. − Tailored porous architectures are attained via innumerable combinations of metal clusters and ligands, leading to their use in various applications, including gas storage, − separation, − catalysis, − sensing, − and drug delivery. , However, MOC arrangements easily collapse during desolvation. As a result, the pore windows of each cage are blocked by adjacent cages, resulting in the loss of porosity; this is a daunting challenge that must be overcome to enable practical applications of MOCs.…”

Magnetic Cu/Co nanoparticles supported on nitrogen‐doped porous carbon derived from Cu/Co@aZIF: Investigation of catalytic activity and structural properties

“…The advantages of the AAC catalytic system catalyzed by Cu/Co@NPC over other MOF-derived catalysts are as follows: (1) requires less catalyst concentration; (2) shorter reaction time; (3) high efficiency with chlorinated substrates; and (4) high reusability. To the best of our knowledge, the Cu/Co@NPC is the only catalyst that combines Cu-MOF 5 mol%, 0.37 mmol, EtOH/H 2 O, rt, 12 h 95 [45] Cu25%/ZIF-8 5 mol% catalyst, 1 mmol, EtOH, 70 C, 3 h 99 [46] Cu(I)-MOF 1 mol% (based on Cu element), 1 mmol, DMF/DMSO, 60 C, 4 h 99 [47] CuI@UiO-67-IM 2 mol%, 1 mmol, H 2 O, 80 C, 2 h 89 [48] Cu-MOF 0.25 mol%, 1 mmol, neat, 50 C, 2.5 h 94 [49] Copper-MOF 0.1 mol%, 1 mmol, EtOH, 70 C, 1 h 99 [50] Cu-MOF 10 mol%, 1 mmol, H 2 O/MeOH, 70 C, 2 h, sodium ascorbate, K 2 CO 3 93 [51] Cu(BTC)-MOF 10 mg, 1.6 mmol, MeOH, rt, 16 h 88 [52] Cu(INA) 2 -MOF 1 mol%, 0.5 mmol, solvent free, 80 C, 4 min 95 [53] MOF-2 1 mol%, 0.1 mmol, H 2 O/CH 3 CN, rt (WLED [24 W]), 8 h 45 [54] Abbreviations: MOF, metal-organic framework; WLED, white light-emitting diode; NPC, Nitrogen-doped porous carbon; DMF, Dimethylformamid; ZIF, Zeolitic imidazolate framework; BTC, benzene-1,3,5-tricarboxylic acid; INA, isonicotinate ion.…”