2014
DOI: 10.1002/chem.201403123
|View full text |Cite
|
Sign up to set email alerts
|

Drastic Enhancement of Catalytic Activity via Post‐oxidation of a Porous MnII Triazolate Framework

Abstract: Mn(III) is a powerful active site for catalytic oxidation of alkyl aromatics, but it can be only stabilized by macrocyclic chelating ligands such porphyrinates. Herein, by using benzobistriazolate as a rigid bridging ligand, a porous Mn(II) azolate framework with a nitrogen-rich coordinated environment similar to that of metalloporphyrins was synthesized, in which the Mn(II) ions can be post-oxidized to Mn(III) to achieve drastic increase of catalytic (aerobic) oxidation performance.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1

Citation Types

3
53
0

Year Published

2016
2016
2023
2023

Publication Types

Select...
5
1

Relationship

0
6

Authors

Journals

citations
Cited by 71 publications
(56 citation statements)
references
References 49 publications
3
53
0
Order By: Relevance
“…Design, synthesis, and gas adsorption properties. In our search for a cooperative, O 2 -selective metal-organic framework, we initially investigated the known framework Co 2 Cl 2 (bbta), which features a high density of coordinatively-unsaturated cobalt(II) ions 31,32 , as well as basic nitrogen-donor ligands that should enhance the reducing potential of the metal centers 24 . However, we found that Co 2 Cl 2 (bbta) exhibits only a weak interaction with oxygen ( Fig.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Design, synthesis, and gas adsorption properties. In our search for a cooperative, O 2 -selective metal-organic framework, we initially investigated the known framework Co 2 Cl 2 (bbta), which features a high density of coordinatively-unsaturated cobalt(II) ions 31,32 , as well as basic nitrogen-donor ligands that should enhance the reducing potential of the metal centers 24 . However, we found that Co 2 Cl 2 (bbta) exhibits only a weak interaction with oxygen ( Fig.…”
Section: Resultsmentioning
confidence: 99%
“…These hydrogen bonding interactions are thought to play a key role in reversible O 2 binding in these proteins, and may also be advantageous for the development of metal-organic frameworks for selective and reversible O 2 capture. Here, we report the detailed characterization of O 2 adsorption in the frameworks Co 2 X 2 (bbta) (X − = Cl − , OH − ) [31][32][33][34] and show that Co 2 (OH) 2 (bbta) is able to capture O 2 with high affinity by leveraging both electron transfer and hydrogen bonding interactions ( Fig. 2c).…”
mentioning
confidence: 94%
“…Thus, to obtain stable MOFs, researchers choose to construct frameworks with carboxylate‐based ligands (hard Lewis bases) and high‐valent metal ions (hard Lewis acids), or azolate‐based ligands (soft Lewis bases) and low‐valency transition metal ions (soft Lewis acids). Guided by this strategy ( Scheme ), dozens of MOFs with excellent stability were obtained …”
Section: Fundamentals Of Mof Stabilitymentioning
confidence: 99%
“…This is further motivated by prior studies of transition metal-oxo complexes,w hich have shown that the presence and identity of coordinating,a nionic ligands can greatly enhance rates of hydrogen atom transfer reactions. [5,31,32] Of the previously synthesized MAFs containing open metal sites,M -BTT, [33] M-BTTri (H 3 BTTri = 1,3,5tri(1H-1,2,3-triazol-5-yl)benzene), [34,35] and M-BDTriP (H 3 BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis-(1H-1,2,3-triazole)) [34] all have m 4 -Cl À ligands,M 2 Cl 2 (BBTA) (H 2 BBTA = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) [36] and M 2 Cl 2 (BTDD) (H 2 BTDD = bis(1H-1,2,3-triazolo [4,5-b],-[4',5'-i])dibenzo [1,4]dioxin)) [37] have m-Cl À ligands,a nd M-MFU-4l (MFU = Metal-Organic Framework Ulm) has terminal Cl À ligands [38,39] that can potentially be exchanged. Postsynthetic ligand exchange in the aforementioned materials has led to the discovery of MOFs with enhanced water uptake, [40] O 2 binding strengths, [41] hydrogen storage properties, [42] and turnover frequencies for CO 2 reduction, [43] among several other applications.…”
Section: Introductionmentioning
confidence: 99%
“…[37,46,47] Perhaps most notably,like several of the aforementioned MAFs,t he M 2 X 2 (BBTA) family is highly tunable,both with regards to the metal identity as well as the bridging monovalent anions connecting each metal center. To date,M 2 Cl 2 (BBTA) ( [36,40,43,[47][48][49][50][51] Forr eference, the pores of these materials are quite large,with diameters of approximately 13 and 23 for M 2 X 2 (BBTA) and M 2 X 2 -(BTDD), respectively. [52] Using DFT,w einvestigate the effects of exchanging the metal cation (M = V, Cr, Mn, Fe,C o, Ni, Cu) and bridging ligand (X = F, Cl, Br, OH, SH, SeH) on the frameworks ability to form reactive metal-oxo motifs for the oxofunctionalization of strong CÀHb onds.W hile some of these combinations of metals and ligands may not yield frameworks capable of forming (meta-)stable metal-oxo motifs,w e include aw ide range of metals and ligands to aid in the identification of overarching structure-property relationships across this family of tunable materials.A sar esult of this study,weshow how the choice of linker and anions within the first coordination sphere can be used to increase the stability of high-valent metal-oxo sites that are reactive toward strong C À Hb onds in the M 2 X 2 (BBTA) family of metal-triazolate frameworks.W ealso use the M 2 X 2 (BBTA) family to demonstrate the important role of electron spin for C À Hb ond activation via terminal metal-oxo species,w hile simultaneously clarifying several questions about the radical-like character of the metal-oxo motif.…”
Section: Introductionmentioning
confidence: 99%