“…4a, b). Significantly, although with lower dosage of TEMPO and base, MFM-100d shows higher activity for alcohol oxidation than all previously reported Cu(II)-MOFs 7,39,40 . These results confirm that integration of mesopores and uncoupled Cu(II) sites in MFM-100d results in its exceptional catalytic performance.Fig.…”
Incorporation of mesopores and active sites into metal-organic framework (MOF) materials to uncover new efficient catalysts is a highly desirable but challenging task. We report the first example of a mesoporous MOF obtained by templated electrosynthesis using an ionic liquid as both electrolyte and template. The mesoporous Cu(II)-MOF MFM-100 has been synthesised in 100 seconds at room temperature, and this material incorporates crystal defects with uncoupled Cu(II) centres as evidenced by confocal fluorescence microscopy and electron paramagnetic resonance spectroscopy. MFM-100 prepared in this way shows exceptional catalytic activity for the aerobic oxidation of alcohols to produce aldehydes in near quantitative yield and selectivity under mild conditions, as well as having excellent stability and reusability over repeated cycles. The catalyst-substrate binding interactions have been probed by inelastic neutron scattering. This study offers a simple strategy to create mesopores and active sites simultaneously via electrochemical formation of crystal defects to promote efficient catalysis using MOFs.
“…4a, b). Significantly, although with lower dosage of TEMPO and base, MFM-100d shows higher activity for alcohol oxidation than all previously reported Cu(II)-MOFs 7,39,40 . These results confirm that integration of mesopores and uncoupled Cu(II) sites in MFM-100d results in its exceptional catalytic performance.Fig.…”
Incorporation of mesopores and active sites into metal-organic framework (MOF) materials to uncover new efficient catalysts is a highly desirable but challenging task. We report the first example of a mesoporous MOF obtained by templated electrosynthesis using an ionic liquid as both electrolyte and template. The mesoporous Cu(II)-MOF MFM-100 has been synthesised in 100 seconds at room temperature, and this material incorporates crystal defects with uncoupled Cu(II) centres as evidenced by confocal fluorescence microscopy and electron paramagnetic resonance spectroscopy. MFM-100 prepared in this way shows exceptional catalytic activity for the aerobic oxidation of alcohols to produce aldehydes in near quantitative yield and selectivity under mild conditions, as well as having excellent stability and reusability over repeated cycles. The catalyst-substrate binding interactions have been probed by inelastic neutron scattering. This study offers a simple strategy to create mesopores and active sites simultaneously via electrochemical formation of crystal defects to promote efficient catalysis using MOFs.
“…It is well-known that the substituent groups attached to the ligand backbones might play an important role in governing the network structures of acid–base mixed-ligand CPs. Numerous mixed-ligand CPs, especially those with transition-metal centers, have been synthesized by selecting N-heterocyclic ligands incorporated with a series of comparable R-terephthalic acids or R-isophthalic acids with different substituents. − In our previous work, we employed Fbtx and phthalate as mixed ligands to prepare a stable Cu(II)-based CP under hydrothermal conditions . To further investigate the ligand effect of CPs, four new Co-CP-R were obtained under both hydrothermal and microwave conditions.…”
Section: Resultsmentioning
confidence: 99%
“…Recently, a mixed-linker synthetic strategy reported by Garcia et al demonstrated that the use of a such ligand tends to endow CPs/MOFs with superior stability and catalytic activity over those with a single ligand . Our group previously developed a stable mixed-linker Cu-CP, with 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtx) as the primary ligand and 1,2-benzenedicarboxylate (1,2-BDC) as the secondary ligand, and found it to be a highly active heterogeneous catalyst for the aerobic oxidation of primary alcohols . Therefore, the investigations on the ligands of CPs would be able to shed light on the development of a high-performance catalyst.…”
Section: Introductionmentioning
confidence: 99%
“…45 Our group previously developed a stable mixed-linker Cu-CP, with 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtx) as the primary ligand and 1,2-benzenedicarboxylate (1,2-BDC) as the secondary ligand, and found it to be a highly active heterogeneous catalyst for the aerobic oxidation of primary alcohols. 46 Therefore, the investigations on the ligands of CPs would be able to shed light on the development of a high-performance catalyst.…”
Section: ■ Introductionmentioning
confidence: 99%
“…47−50 In our previous work, we employed Fbtx and phthalate as mixed ligands to prepare a stable Cu(II)-based CP under hydrothermal conditions. 46 To further investigate the ligand effect of CPs, four new Co-CP-R were obtained under both hydrothermal and microwave conditions. The hydrothermal reactions of Co(OAc) 2 •4H 2 O with Fbtx and 4-R-1,2-H 2 BDC (R = F, Cl, Br, CF 3 ) at 130 °C for 3 days followed by a standard workup produced pink crystals of Co-CP-F (49.2% yield), Co-CP-Cl (44.8% yield), Co-CP-Br (42.1% yield), and Co-CP-CF 3 (40.4% yield), respectively, where the 1:1.5:1 molar ratio of Co/Fbtx/1,2-BDC derivative was retained.…”
Regulating the chemical/thermal stability and catalytic activity of coordination polymers (CPs) to achieve high catalytic performance is topical and challenging. The CPs are competent in promoting oxidative cross-coupling, yet they have not received substantial attention. Here, the ligand effect of the secondary ligand of CPs for oxidative cross-coupling reactions was investigated. Specifically, four new isostructural CPs [Co(Fbtx) Cl, Br, CF 3 ) were prepared. It was found that in the reactions of oxidative amination of benzoxazoles with secondary amines and the oxidative coupling of styrenes with benzaldehydes, both the chemical and thermal stabilities of the four Co-CPs with the R group followed the trend of −CF 3 > −Br > −Cl > −F. Density functional theory (DFT) calculations suggested that the difference in reactivity may be ascribed to the effect of substituent groups on the electron transition energy of the cobalt(II) center of these Co-CPs. These findings highlight the secondary ligand effect in regulating the stability and catalytic performance of coordination networks.
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