Framework functionalisation triggers metal complex binding

Ingleson, Michael J.; Barrio, Jorge Pérez; Guilbaud, Jean‐Baptiste; Khimyak, Yaroslav Z.; Rosseinsky, Matthew J.

doi:10.1039/b718367d

Cited by 292 publications

(171 citation statements)

References 21 publications

(27 reference statements)

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“…The authors carried out a preliminary catalytic investigation on this modified MOF structure for the oxidation of cyclohexene with TBHP as the oxidant. However, the VO(acac) 2 @IRMOF-3 showed a rather low catalytic activity and stability 104 . The group of Ahn reported a more straightforward one step functionalization of the IRMOF-3 with a manganese complex (entry 21 Table 4) 105 .…”

Section: Pom@mofmentioning

confidence: 95%

“…A similar mechanism was proposed (Scheme 7) with the generation of phthalimide N-oxyl radicals acting as precursors of C-centered radicals that would undergo auto-oxidation. Ingleson et al 104 reported the two steps modification of IRMOF-3 to an imine grafted VO(acac) 2 complex (entry 20 Table 4). The authors carried out a preliminary catalytic investigation on this modified MOF structure for the oxidation of cyclohexene with TBHP as the oxidant.…”

Section: Pom@mofmentioning

confidence: 99%

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Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts. The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a "ship-in-a-bottle" complex. As the pore size, pore shape and functionality of MOFs can be designed in numerous ways, shape selectivity and even chiral selectivity can be created. In this review, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.

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Section: Pom@mofmentioning

confidence: 95%

Section: Pom@mofmentioning

confidence: 99%

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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“…14 In addition, functionalization with aromatic -NH 2 groups may facilitate metal complex binding, as demonstrated by M. J. Ingleson et al 15 However, the utilization of these functionalized MOFs as catalysts in the dehydrogenation of AB aqueous solution has rarely been reported.…”

Section: Introductionmentioning

confidence: 99%

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

2018

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Well-dispersed ruthenium nanoparticles (Ru NPs) are immobilized within the pores of amine-functionalized MIL-53 via an in situ impregnation-reduction method. The resulting Ru/MIL-53(Al)-NH 2 catalyst exhibits superior catalytic performance for the dehydrogenation of ammonia borane (AB) at ambient temperature relative to the Ru/MIL-53(Al) catalyst; it has a turnover frequency (TOF) of 287 mol H 2 min À1 (mol Ru) À1and an activation energy (E a ) of 30.5 kJ mol À1 . The amine groups present in the MIL-53(Al)-NH 2 framework facilitate the formation and stabilization of ultra-small Ru NPs by preventing their aggregation. Additionally, the Ru/MIL-53(Al)-NH 2 catalyst exhibits satisfactory durability and reusability:72.4% and 86.3% of the initial catalytic activity was maintained after the fifth successive cycle of the hydrolytic dehydrogenation of AB in the two respective tests.

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“…In principle, three different ways are used for the functionalisation: (1) functional groups (e.g. -NH 2 , -NO 2 , -N 3 ) react with another reactive molecule inside the pores, [20][21][22][23][24] (2) coordinative unsaturated sites are used, 25 and (3) nucleophilic substitution takes place at the aromatic ring. 26 Important requirements for the post-synthetic modification are a high chemical stability and large, accessible pores of the host material.…”

Section: Introductionmentioning

confidence: 99%

Introducing a photo-switchable azo-functionality inside Cr-MIL-101-NH2 by covalent post-synthetic modification

et al. 2012

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For the first time an azo functionality was covalently introduced into a MOF by post-synthetic modification. The reaction of Cr-MIL-101-NH 2 with p-phenylazobenzoylchloride (1) and 4-( phenylazo)-phenylisocyanate (2) as the reactants led to the compounds Cr-MIL-101_amide and Cr-MIL-101_urea, with the azo groups protruding into the mesoporous cages. XRPD and N 2 sorption measurements confirm the intactness of the framework and the successful covalent modification was proven by IR-and NMRspectroscopy. Furthermore, cis/trans isomerisation upon irradiation with light was demonstrated by UV/ Vis spectroscopy. More distinct changes in the UV/Vis spectra were observed for Cr-MIL-101_amide compared to Cr-MIL-101_urea, while the degree of functionalization, i.e. the number of reacted NH 2 -groups, seems to have a less pronounced effect. The variation of the sorption properties due to the cis/trans isomerisation was proven by methane adsorption measurements.

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Framework functionalisation triggers metal complex binding

Abstract: Post-synthetic derivatisation of a porous material produces a functionalized material that binds the metal complex V(O)acac2, in contrast to the unfunctionalized precursor, which is inactive for complex binding.

Cited by 292 publications

References 21 publications

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

Introducing a photo-switchable azo-functionality inside Cr-MIL-101-NH2 by covalent post-synthetic modification

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