A Calix[4]resorcinarene-Based [Co₁₂] Coordination Cage for Highly Efficient Cycloaddition of CO₂ to Epoxides

Abstract

The design and synthesis of polynuclear metal cluster-based coordination cages is of considerable interest due to their appealing structural characteristics and potential applications. Herein, we report a calix[4]resorcinarene-based [Co 12 ] coordination cage, [Co 12 (TPC4R-I) 2 (1,3-BDC) 10 (μ 3 -OH) 4 (H 2 O) 10 (DMF) 2 ]•7DMF•23H 2 O (1), assembled with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3benzenedicarboxylates (1,3-BDC), and 12 Co(II) cations. Remarkably, it is shown to be a highly efficient recyclable heterogeneous catalyst for CO 2 conversion due to its exposed Co(II) Lewis acid sites.

Facile Green Synthesis of New Copper-Based Metal–Organic Frameworks: Experimental and Theoretical Study of the CO2 Fixation Reaction

“…[6][7][8][9][10][11][12] Additionally, the selective coupling between CO 2 and epoxides to produce cyclic carbonates has also attracted significant attention in this area because of its wide applications (Scheme 1). [13][14][15][16][17][18][19][20][21][22][23][24][25] However, the use of catalysts and co-catalysts under low temperature and pressure conditions is challenging for the cycloaddition reactions. One solution is to design catalytic systems that can easily attract and activate CO 2 , which will allow them to be used at low reaction temperatures and ambient pressures.…”

Supramolecular Assemblies of Sulfonatomethylated Calix[4]resorcinarenes with Aquated Sodium(I), Cesium(I), and Aluminum(III) Ions

“…Among them, p ‐sulfonatocalix[4]arene has been successfully synthesized and used in the construction of coordination complexes in both solution and the solid state [14–19] . Calix[4]resorcinarene, as a special subset of calix[4]arene, has been recognized to be an important class of supramolecular compounds with a bowl‐shaped aromatic cavity [20−22] . In this case, their upper and lower rims could be modified with various functional groups, which greatly enriched the structural diversities of their coordination polymers.…”

Self‐Assembly of Polyoxometalate‐Resorcin[4]arene‐Based Inorganic‐Organic Complexes: Metal Ion Effects on the Electrochemical Performance of Lithium Ion Batteries

“…In this respect, calix[4]arenes, showing bowl‐shaped cavities, can be easily modified to show intriguing structures [30–38] . Over the past decade, our groups have been engaging in the modification of calix[4]arenes with various functional groups, such as 4‐(pyridin‐2‐yl)pyrimidine‐2‐thiolate, [29] 2‐(4 H ‐pyrazol‐3‐yl)pyridine, [33] and 2‐mercaptopiperidine [39] .…”

“…In this respect, calix [4]arenes, showing bowl-shaped cavities, can be easily modified to show intriguing structures. [30][31][32][33][34][35][36][37][38] Over the past decade, our groups have been engaging in the modification of calix [4]arenes with various functional groups, such as 4-(pyridin-2-yl)pyrimidine-2-thiolate, [29] 2-(4H-pyrazol-3yl)pyridine, [33] and 2-mercaptopiperidine. [39] And numerous Inorganic-organic hybrid complexes or cages with elegant structures have been acquired by the assembly of functionalized calix [4]arenes, metal ions and POMs.…”