Synthesis, X-ray crystal structure and spectroscopic characterization of heterotrinuclear oxo-centered complex [Fe2NiO(CH3CH2COO)6(H2O)3]

Yazdanbakhsh, Mohammad; Tavakkoli, Haman; Taherzadeh, Maryam; Boese, Roland

doi:10.1016/j.molstruc.2010.08.029

Cited by 13 publications

(5 citation statements)

References 26 publications

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“…In the IR spectrum of the Fe 2 CoO, Fe 2 NiO, and Fe 2 CrO clusters, the characteristic stretching vibration observed for the Fe 3 (μ 3 -O) core (at ∼600 cm –1 ) disappears, and two new bands appear. This is due to a reduction in the site geometry from D 3 h to C 2 v upon metal substitution, which lifts the degeneracy of the asymmetric metal-μ 3 -oxo stretching vibrations. − More detailed analysis is discussed in the Supporting Information (Figure S6).…”

Section: Resultsmentioning

confidence: 99%

Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Peng

Asgari

Miéville

et al. 2017

ACS Appl. Mater. Interfaces

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Metal-organic frameworks (MOFs) have attracted much attention in the past decade owing to their unprecedented internal surface areas, tunable topologies, designable surfaces, and various potential applications. One bottleneck in the field regarding MOF synthesis is controlling the metal-containing secondary building unit (SBU) incorporated into the structure. In this work we report the synthesis and characterization of five trimeric [M(μ-O)(CHCO)] clusters (where M = Fe, Cr, Fe/Cr, Fe/Co, or Fe/Ni and x = +1 or 0). The monocarboxylate capping ligand, acetate in this case, readily undergoes exchange with several difunctional counterparts, including 1,4-benzenedicarboxylic acid (H-BDC) and biphenyl-4,4'-dicarboxylic acid (H-BPDC), for the formation of an isostructural series of MOFs, several of which are newly reported (for M = Fe/Cr, Fe/Co, and Fe/Ni) and show excellent CO adsorption properties. In this report, a host of techniques including NMR, ICP, and ESI-MS are used to probe the ligand exchange process and composition of the SBUs, and XAS is used to monitor the Fe and Cr environment throughout the reactions, giving strong evidence that the clusters stay intact throughout the MOF synthesis. This work reveals that predefined SBUs is an effective means to create metal-substituted analogues of known frameworks. Further, CO adsorption and in situ IR are used to probe accessibility of the metals after solvent removal. We show for the first time that the incorporation of the neutral clusters, containing weaker Lewis acids like Ni and Co, can promote the formation of open metal sites in the MOF frameworks, structural features known to enhance the binding energy of small guest molecules like CO.

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Section: Resultsmentioning

confidence: 99%

Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Peng

Asgari

Miéville

et al. 2017

ACS Appl. Mater. Interfaces

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“…The FTIR spectrum of MIL-88B was in agreement with previous reports. The vibration of Fe 3 (μ3-O) is seen at 620 cm −1 [51] . The peaks due to symmetric and asymmetric C=O vibrations of the organic linkers and that of C–O of the carboxyl group are observed at 1660 cm −1 and 1398 cm −1 , respectively [52] .…”

Section: Discussionmentioning

confidence: 99%

A quest for cytocompatible metal organic frameworks in non-viral gene therapy: Relevance of zeolitic imidazolate framework-8

Poddar¹,

Pyreddy²,

Polash³

et al. 2022

Biomaterials and Biosystems

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“…There are four remarks: (i) no free acid (no band at 1700 cm −1 ) is found, (ii) the value Δ = ν asym (OCO) − ν sym (OCO) corresponds well to the bridge coordination mode of metal carboxylates, 31 ) is observed, while the vibration of Fe 3 (μ 3 -O) (620 cm −1 ) is only noticed in the single metal Fe 3 -MIL-88B sample. 37,38 The UV-Vis spectra of the Fe 2 Ni-MIL-88B samples with different terminal ligands are shown in Fig. 2.…”

Section: Synthesis Of Mixed Metalmentioning

confidence: 99%

Synthesis and engineering porosity of a mixed metal Fe₂Ni MIL-88B metal–organic framework

2013

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A new rational approach has been developed for the synthesis of a mixed metal MIL-88B metal-organic framework based on a neutral mixed metal cluster, such as Fe(2)Ni(μ(3)-O). Unlike the conventional negative charged single metal cluster, the use of the neutral mixed metal cluster as nodes in the framework avoids the need of a compensating anion inside the porous MIL-88B system; thus the mixed metal MIL-88B becomes porous. The flexibility of the mixed metal MIL-88B can be controlled by terminal ligands with different steric hindrance. This allows us to reversibly customize the porosity of the MIL-88B structure at three levels of specific surface area as well as the pore volume.

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Synthesis, X-ray crystal structure and spectroscopic characterization of heterotrinuclear oxo-centered complex [Fe2NiO(CH3CH2COO)6(H2O)3]

Cited by 13 publications

References 26 publications

Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

A quest for cytocompatible metal organic frameworks in non-viral gene therapy: Relevance of zeolitic imidazolate framework-8

Synthesis and engineering porosity of a mixed metal Fe₂Ni MIL-88B metal–organic framework

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Synthesis, X-ray crystal structure and spectroscopic characterization of heterotrinuclear oxo-centered complex [Fe2NiO(CH3CH2COO)6(H2O)3]

Cited by 13 publications

References 26 publications

Using Predefined M3(μ3-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Using Predefined M3(μ3-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

A quest for cytocompatible metal organic frameworks in non-viral gene therapy: Relevance of zeolitic imidazolate framework-8

Synthesis and engineering porosity of a mixed metal Fe2Ni MIL-88B metal–organic framework

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Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Using Predefined M₃(μ₃-O) Clusters as Building Blocks for an Isostructural Series of Metal–Organic Frameworks

Synthesis and engineering porosity of a mixed metal Fe₂Ni MIL-88B metal–organic framework