Synthesis, Structure, and Selected Properties of Aluminum-, Gallium-, and Indium-Based Metal-Organic Frameworks

Schilling, Lars-Hendrik; Reinsch, Helge; Stock, Norbert

doi:10.1002/9783527693078.ch5

Cited by 9 publications

(9 citation statements)

References 153 publications

(228 reference statements)

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“…In the past few years a large number of porous metal–organic frameworks (MOFs) based on trivalent aluminum cations have been reported. − The increasing interest in these compounds is due to their high thermal and chemical stability . Furthermore, Al 3+ salts are commercially available, which makes the synthesized MOF materials interesting for industrial applications .…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, Al 3+ salts are commercially available, which makes the synthesized MOF materials interesting for industrial applications . The high stability allows postsynthetic modification (PSM) to introduce versatile functional groups to the MOF framework. − The use of prefunctionalized linker molecules is an alternative way to vary the chemical and physical properties of the pore walls in order to tune the sorption behavior and to allow for PSM. − From a chemist’s point of view the use of aluminum for MOF synthesis is interesting and quite challenging at the same time, due to its rich aqueous solution chemistry. , The diversity of inorganic building units (IBUs) in Al-MOFs − ,, leads in combination with the virtually limitless possible organic linker molecules to various framework structures . In Al-MOFs, solely octahedral coordination of the Al 3+ cations has been identified, and with the exception of CAU-4 only IBUs containing corner- and/or edge-sharing AlO 6 polyhedra have been reported.…”

Section: Introductionmentioning

confidence: 99%

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Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

et al. 2017

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The in situ and systematic high-throughput investigation of the system Al/4,4'-benzophenonedicarboxylic acid (HBPDC)/DMF/HO in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO polyhedra forming the inorganic building unit (IBU). These {AlO} IBUs are arranged in a bcu packing and connected via BPDC ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO polyhedra connected by BPDC ions. Replacing HBPDC by 4,4'-oxydibenzoic acid (HODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N and CO, while the latter only adsorb CO.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

et al. 2017

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“…Further, the addition of modulators controls such a coordination environment and stabilizes the nitrate-bound metal center. − It is to be noted that only a few examples of indium-SBU in the indium organic framework (InOF) are observed (Chart ). − To incorporate luminescence in the MOF, we prepared the linker, 2,4,5-tris(4-carboxy-phenyl)-1-methyl imidazole (H 3 Imtb), a derivative of lophine. − Herein, we report the thermally and hydrolytically stable nanoporous InOF having a uniform cuboctahedral [In 36 (μ-OH) 24 (NO 3 ) 8 (Imtb) 24 ] cage. The SBU comprises pyramidal NO 3 – ions bridged between In 3 (μ-OH) 2 units like 3.111 in organophosphonates (Chart S2).…”

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Cuboctahedral [In₃₆(μ-OH)₂₄(NO₃)₈(Imtb)₂₄]MOF with Atypical Pyramidal Nitrate Ion in SBU: Lewis Acid–Base Assisted Catalysis and Nanomolar Sensing of Picric Acid

Sachan

Anantharaman

2021

Inorg. Chem.

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A robust and multifunctional cuboctahedral [In 36 (μ-OH) 24 (NO 3 ) 8 (Imtb) 24 ] MOF (In(Imtb)-MOF) with an atypical pyramidal nitrate ion-containing hitherto unknown SBU core [In 9 (μ-OH) 6 (NO 3 )] is reported. The intra-and interlayer nitrate ions adopt pyramidal and inverted pyramidal shapes, which separates the active indium site [(In 3 (μ-OH) 2 )NO 3 -(In 3 (μ-OH) 2 )] and linear In 3 (μ-OH) 2 by 0.5 and 0.9 nm, respectively. Additionally, the high density of active metal sites shows remarkable catalytic activity with higher TOF even for sterically hindered substrates in Strecker synthesis and CO 2 cycloaddition. Moreover, the luminescence behavior of In(Imtb)-MOF and the presence of uncoordinated nitrogen atoms are exploited for selective sensing of explosive trinitrophenol (TNP) with a detection limit (LOD) of 2.3 ppb.

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“…Most of the reported group 13 element MOFs feature rigid carboxylates as bridging ligands. 14,27 Although MOFs with N-donor linkers are rare, the formation of different coordination compounds ranging from 1D coordination polymers to 2D and 3D ionic coordination networks was reported. 14,28–36…”

Section: Introductionmentioning

confidence: 99%

Coordination polymers and molecular complexes of group 13 metal halides with bis-pyridylethane: comparison with rigid N-containing ligands

et al. 2022

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Synthesis, Structure, and Selected Properties of Aluminum-, Gallium-, and Indium-Based Metal-Organic Frameworks

Cited by 9 publications

References 153 publications

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

Cuboctahedral [In₃₆(μ-OH)₂₄(NO₃)₈(Imtb)₂₄]MOF with Atypical Pyramidal Nitrate Ion in SBU: Lewis Acid–Base Assisted Catalysis and Nanomolar Sensing of Picric Acid

Coordination polymers and molecular complexes of group 13 metal halides with bis-pyridylethane: comparison with rigid N-containing ligands

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Synthesis, Structure, and Selected Properties of Aluminum-, Gallium-, and Indium-Based Metal-Organic Frameworks

Cited by 9 publications

References 153 publications

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization

Cuboctahedral [In36(μ-OH)24(NO3)8(Imtb)24]MOF with Atypical Pyramidal Nitrate Ion in SBU: Lewis Acid–Base Assisted Catalysis and Nanomolar Sensing of Picric Acid

Coordination polymers and molecular complexes of group 13 metal halides with bis-pyridylethane: comparison with rigid N-containing ligands

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Cuboctahedral [In₃₆(μ-OH)₂₄(NO₃)₈(Imtb)₂₄]MOF with Atypical Pyramidal Nitrate Ion in SBU: Lewis Acid–Base Assisted Catalysis and Nanomolar Sensing of Picric Acid