Manganese MOFs

Mn3Ca20g, Calcium manganese oxide, 22 73 MoF,OK2, Molybdate(V), pentafluorooxo, dipotassium, 21 170... 

Also interesting is the Mn(II) D-saccharide MOF ([Mn2(sac)2(H20)2] with H2sac = D-saccharic acid) with chiral helicity and redox activity centered on manganese. In this structure hydrophilic channels have been identified and two distinct redox processes (see Fig. 9) have been observed in distilled water but so far not further investigated. 

It is a critical aspect to obtain porphyrinic frameworks that have both permanent porosity and internally accessible active sites for catalytic application. The Flupp group reports an extended family of porphyrinic MOFs that directly incorporate divers metal ions of AF+, Zn +, Pd " ", Mn +, and Fe + in porphyrins. The active sites in the large channels of these robust porphyrinic materials (RPMs) are readily accessible to substrate molecules. As an illustrative example, the manganese-containing RPM is catalytically competent for oxidation of styrene and cyclohexane. ZnMn-RPM is much superior to the homogeneous counterpart 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-MnCl (TPFPP(MnCl)) in term of the catalytic activity and stability. 

Champness and coworkers prepared the complexes c-[M(bpydc)(CO)3X] (M = Mn, Re bpydc = 2,2 -bipyridine-5,5 -dicarboxylate) and reacted them with manganese(II) to form MOFs in which Mn(II) cations are the nodes and the diimine complexes are the linkers. On treatment with UV radiation, fac to mer isomerization was observed, as witnessed by IR spectroscopy and X-ray crystallography. ... 

Ahn and coworkers showed that it was possible to combine the PSM of an amine to form an imine-based ligand and coordination of a metal to this into a single step. They reported that lRMOF-3 reacts with [Mn(acac)2] to form a catalytically active manganese-functionalized MOF (equation 21). ... 

Figure 2 The illustration of some representative UMCs. (a) A dicopper paddlewheel structure with unsaturated copper centers. (b) A Co4(p4-O)(carboxylate)g SBU with unsaturated cobalt centers. (c) A metalloporphyrin moiety with unsaturated iron center."" (d) A Mn4(p4-Cl)(tetrazolate)g SBU with unsaturated manganese centers." (e) The Mg-MOF-74 (CPO-27) structure with unsaturated magnesium centers ...

Metal porphyrins are widely used as molecular catalysts both in synthetic systems and as active sites in many metal enzymes. The first report on the use of porphyrins as ligands for catalytically active MOFs refers to the PIZA-3 (Porphyrinic Illinois Zeolite Analogue) system [134], In this MOF structure, trinuclear manganese clusters are the nodes, and [tetrakis(phenylcarboxylate)porphyrin]Mn(lll) complexes are the ligands. PlZA-3 has a... 

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