The effect of substituted benzene dicarboxylic acid linkers on the optical band gap energy and magnetic coupling in manganese trimer metal organic frameworks

Asha, K. S.; Reber, Arthur C.; Ahmed, N.; Nath, R.; Mandal, Sukhendu

doi:10.1039/c6tc03577a

Cited by 10 publications

(9 citation statements)

References 41 publications

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“…Clearly, a redshift occurred for the MOFs with electron-donating groups such as OH, NH 2 , or CH 3 . Because no DFT calculations containing density of state have been reported for rigid (MIL-101, MIL-126) or flexible (MIL-53, MIL-88) iron MOFs, the explanation for the band gap reduction was apprehended using current knowledge on MOFs such as MIL-125(Ti), , IRMOF(Zn), UiO-66(Zr), , and Mn-based MOFs …”

Section: Resultsmentioning

confidence: 99%

“…Because no DFT calculations containing density of state have been reported for rigid (MIL-101, MIL-126) or flexible (MIL-53, MIL-88) iron MOFs, the explanation for the band gap reduction was apprehended using current knowledge on MOFs such as MIL-125(Ti), 53,54 IRMOF(Zn), 55 UiO-66(Zr), 56,57 and Mn-based MOFs. 58 Generally, when an electron-donating group, be it via resonance (also called mesomeric "+ M") or inductive ("+I") effect, is introduced, a shrinkage of the band gap is observed. By pushing electrons toward the aromatic ring, the highest occupied molecular orbital is destabilized and an increase in its energy is observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Linker Engineering of Iron-Based MOFs for Efficient Visible-Light-Driven Water Oxidation Reaction

et al. 2019

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Iron-based metal-organic frameworks (MOFs) have been reported to display notable activity for photocatalytic water oxidation reaction (WOR). Previous reports published managed to grasp some of the important structural factors to develop activity, but no rigorous study has been accomplished toward the impact of the organic linkers on the WOR photoactivity. In this study, nine MOFs of the MIL-88B structure with different linkers were synthesized. The linkers were separated into two categories: those with electron-donating groups and those with electron-withdrawing substituents. MOFs fabricated from the latter linkers exhibited higher efficiency for WOR compared to the former, even though they demonstrated a lower visible light absorption ability. It was considered that the difference in reactivity originated from side reactions of the linkers toward reactive intermediates created during WOR, such as hydroxyl radical (OH•). Hydroxylation of terephthalic acid during WOR was confirmed by 1H NMR. Since the highest activity, five times greater than pristine MIL-88B, was obtained from tetrafluoroterephthalic acid-based MIL-88B, it was concluded that adding electron-withdrawing groups could prevent or slow the hydroxylation rate of the linkers by reducing the electron density of the benzene ring, thus promoting the photocatalytic WOR reaction.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Linker Engineering of Iron-Based MOFs for Efficient Visible-Light-Driven Water Oxidation Reaction

et al. 2019

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“…The synthesis of semiconductor hybrid materials is in high demand. It was proved that HOMO is located on the organic ligand and LUMO mainly on the metal node, , so conjugation and functionalization of the organic ligand may affect the HOMO position. These types of hybrid structures exhibit flat conduction and valence bands which lead to the indirect band gap .…”

Section: Resultsmentioning

confidence: 99%

Series of Mn(II)/Mg(II)/Zn(II) Coordination Polymers with Azo/Alkene Functionalized Ligands

Asha

Mandal

2018

Crystal Growth & Design

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A series of six novel coordination polymers based on Mn(II)/ Mg(II)/Zn(II) metal ions with azo/alkene functionalized carboxylic acid have been synthesized and well-characterized using several state-of-art techniques. Compound 1, {[Mn 2 (ABDCA) 2 (DPE)(DMF) 2 ]•2DMF} n , (where ABDCA = Azobenzene-4,4′-dicarboxylic acid, DPE = 1,2-Di(4-pyridyl)ethylene, and DMF = N,N′-Dimethylformamide) is a three-dimensional structure with threefold interpenetration. Compound 2, {[Mn 3 (ABDCA) 3 (DMF) 4 ]•2DMF} n contains Mn 3 O 16 cluster unit which is connected with ABDCA ligands to form a twodimensional layered structure. Compound 3, {[Mg 3 (ABDCA) 3 (DMF) 4 ]•4DMF} n contains Mg 3 O 16 clusters, associated with ABDCA ligands, forming the 3D structure. Coordination polymers 4 and 5 ({[Zn(ABDCA)(2,2′-BPy)]•H 2 O} n , (4), {[Zn(SDCA)(2,2′-BPy]} n , ( 5)), respectively, (where SDCA = stilbene-4,4′dicarboxylic acid and 2,2′-BPy = 2,2′-Bipyridine) are identical structures with a difference in carboxylate ligand. In both cases, the one-dimensional chains are π-stacked through 2,2′-bipyridine molecules to form the supramolecular three-dimensional structure. Compound 6 ({[Zn(4,4′-BPy)(ABDCA)]•DMF} n (where 4,4′ BPy = 4,4′-Bipyridine) adopts three-dimensional architecture with fivefold interpenetration. Photoluminescence studies showed that all these compounds were emissive due to either intraligand or ligand to metal charge transfer. Optical band gap energy measurements showed that the values are less for ABDCA based compound compared to SDCA based compounds, and this is due to the difference in the HOMO−LUMO gap in the corresponding ligands. The magnetic measurements of compounds 1 and 2 showed that 1 behaves weakly antiferromagnetic while 2 as paramagnetic.

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“…Solid 1 has a band gap of 1.07 eV, and the solids 2 and 3 have band gaps of 0.8 eV, which falls in the range of reported band gap values for manganese(II)-based CPs. 47,48 In the experimental crystal structures, the solvent molecules, H 2 O, DMF, and DMSO are present, which aid in stabilizing the crystal structures by satisfying the coordinations of the Mn 2+ centers, through oxygen ions and H-bonding between the 2D sheets, with the carboxylate group of bpdc ligand. However, the magnetically interacting Mn−O−Mn unit propagates along the [010] direction not through the solvent molecule(s).…”

Section: ■ Computational Methodsmentioning

confidence: 99%

Influence of Noncovalent Interactions on the Magnetic Behavior of Three Isostructural Layered Manganese(II) Dicarboxylate-Based Coordination Polymers

Singh

Mazumder

Balendra

et al. 2022

Crystal Growth & Design

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Three new isostructural manganese coordination polymers, [Mn(H 2 O)(bpdc)] (1), [Mn(DMF)(bpdc)] (2), and [Mn-(DMSO)(bpdc)] (3) (bpdc = benzophenone-4,4′-dicarboxylate), have been successfully crystallized employing solvent variation. A single crystal X-ray diffraction study revealed that the three solids built of manganese polyhedron (square pyramidal in 1 and octahedral in 2 and 3) extended into two-dimensional sheets through manganese carboxylate coordination interaction. The packing of the layers, however, was greatly influenced through hydrogen bonding exerted by the coordinated solvent molecules (H 2 O, DMF, and DMSO) occupying the apical position of the manganese polyhedron. Low-temperature antiferromagnetic interactions arising due to coupling between the adjacent Mn 2+ ions showed a strong correlation with the variation in the packing of the layers. First-principles calculations of the electronic structures of the solids in terms of singlet (S = 0 with Noodleman's Broken Symmetry) and triplet (S = 1) states showed the superexchange interaction energies to be −0.24, −0.12, and −0.18 eV, respectively, for 1, 2, and 3; the magnetic exchange coupling variation is in correspondence with the decrease in H-bonding interaction holding the layers: H 2 O < DMSO < DMF. The paper also postulates a mechanistic pathway for the observed crystal packing in terms of supramolecular condensation of 1:1 manganese dicarboxylate complexes through a combination of coordination and H-bonding interactions.

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The effect of substituted benzene dicarboxylic acid linkers on the optical band gap energy and magnetic coupling in manganese trimer metal organic frameworks

Abstract: The optical band gap energy and magnetism of a series of Mn based compounds were tuned through linker modification.

Cited by 10 publications

References 41 publications

Linker Engineering of Iron-Based MOFs for Efficient Visible-Light-Driven Water Oxidation Reaction

Linker Engineering of Iron-Based MOFs for Efficient Visible-Light-Driven Water Oxidation Reaction

Series of Mn(II)/Mg(II)/Zn(II) Coordination Polymers with Azo/Alkene Functionalized Ligands

Influence of Noncovalent Interactions on the Magnetic Behavior of Three Isostructural Layered Manganese(II) Dicarboxylate-Based Coordination Polymers

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