Ambient Chemical Fixation of CO₂ Using a Robust Ag₂₇ Cluster‐Based Two‐Dimensional Metal–Organic Framework

Abstract

Unprecedented double S 2À templated Ag 27 clusters have been stabilized by 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP-H 2)l igands to affordarobust 2D metal-organic framework (Ag27-MOF). This silver cluster-assembled material serves as ah ighly efficient heterogeneous catalyst for the cyclization of both terminal and internal propargylamines with CO 2 under atmospheric pressure.D ensity functional theory (DFT) calculations illustrate that the high catalytic activity and broad substrate scope are attributable to the saddle-shaped metallic node in Ag27-MOF,w hichf eatures an accessible platform with high-density silver atoms as p-Lewis acid sites for activating C Ctriple bonds.Asaresult, different sterically hindered alkyne substrates can be effectively activated through p-interactions with these cationic silver centers.

Design, Synthesis and Photoluminescence Sensing Property of a Ni‐Organic Material Achieved from 2,6‐Di(1H‐imidazol‐1‐yl) Naphthalene and Carboxylic Acid Ligands

“…As shown in Figure 6, a gradual decrease of the emission intensity with the increasing addition of acetone, when the acetone concentration is 160 μL, the emission intensity almost disappears [28–29] . As can be seen from Figure 7, with the gradual increase of acetone content, the luminescence intensity of the complex gradually weakens, and the decreasing trend of 1 luminescence conforms to first‐order exponential attenuation, indicating that the luminescence quenching of 1 is controlled by acetone diffusion [30–32] . Subsequently, we used the Stern‐Volmer equation, ( I 0 / I )= K sv [M]+1 to calculate the quenching constant ( K sv ).…”

Precisely Constructed Silver Active Sites in Gold Nanoclusters for Chemical Fixation of CO2

“…Metal nanoclusters with precise formulas and crystallographically determined structures, which may build a bridge between single‐atom catalysts and nanoparticles, have become possible to unravel contributions of single atom or a group of atoms in a nanocluster to its overall catalytic performances [9–12] . For example, surface atom reconstruction of an Au 9 induced by a single Pd atom substitution modulated its active sites following a drastic change for catalytic properties [13, 14] .…”

Diffusion Control in Single-Site Zinc Reticular Amination Catalysts

“…In order to improve the sustainability and innovate in the catalysis of organic transformations, different approaches such as the use of ionic liquids, nanocages, coordination networks or metal-organic frameworks (MOFs) are bridging the gap between traditional homogeneous and heterogeneous catalysts. [6][7][8][9][10][11][12][13][14] The incorporation of Zn(II) as a single site (well-positioned and separated) in open frameworks as zeolites, coordination polymers or MOFs would permit translating this reactivity to the heterogeneous phase for simple separation of the product, thus avoiding its contamination. [15][16][17][18][19][20][21] Pioneering studies of copper active sites in MOFs for Narylations of aryl bromides with aromatic amines and Nheterocycles using Ullmann-type couplings have been reported.…”