Pore modulation of guest photophysics in metal organic frameworks: Photophysical studies of meso-tetra (N-methyl-4-pyridyl) porphine encapsulated within MOM-11 and MOM-12

Alanazi, Abdulaziz A.; Wojtas, Łukasz; McKeithan, Cristopher R.; Larsen, Randy W.

doi:10.1016/j.jphotochem.2019.112329

Cited by 13 publications

(9 citation statements)

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“…The bathochromic shift for these complexes arises from a distortion of the porphyrin ring that allow for the ring nitrogen σ orbitals to interact with metal orbitals as well as overlap between the metal d-π orbitals and the porphyrin anti-bonding π* orbitals which lowers the energy of the porphyrin LUMO [27]. The absorption spectrum of the heterogeneous P(NaAMPS-co-AN)-[Mn(TMPyP)] is similar to that of [MnCl(TMPyP)] +4 with a red shift to 474 nm, 595 nm and 640 nm due to the presence of the same functional groups and interaction between the porphyrin and p(NaAMPS-co-AN) functional groups [28]. To determine the swelling behavior of p(NaAMPS-co-AN)-[Mn(TMPyP)] hydrogels, distillation water was chosen as the swelling media.…”

Section: Synthesis and Characterizationmentioning

confidence: 96%

Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Reusable Manganese Porphyrin under Mild Aqueous Conditions

Sokhandan-Koirim

Ghorbanloo

Mokary-Yazdely

2022

Preprint

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The present study aims to introduce a new catalytic system, namely poly[(2-acrylamido-2-methyl-1-propane sulfonic acid-co-acrylonitrile)-Mn(III) meso tetra(N-methyl-4-pyridyl) porphine briefly called p(NaAMPS-co-AN)‐[Mn(TMPyP)]. Free-radical polymerization at ambient temperature was employed to construct this catalytic system. To prepare this heterogeneous bi-phasic catalyst, poly(NaAMPS-co-AN) was axially grafted onto the metal centers of the MnIII composite. In order to identify the amounts of metals in prepared compound, atomic absorption spectroscopy (AAS) was utilized. The results indicated that p(NaAMPS-co-AN)‐[Mn(TMPyP)] had the potential to efficiently catalyze alcohol oxidation with high selectivity in the solid-liquid biphasic reaction system. Furthermore, the catalytic activities of alcohol oxidation by the reaction-controlled phase transfer catalyst system were compared in the presence of H2O2 and TBHP, as oxidants, in a biphasic environment. It was found that functioning as a nanoreactor, the prepared catalyst system facilitated the oxidation of alcohols in water, leading to the substantial acceleration of catalytic reaction rates. After the completion of the catalytic activity, the catalyst could be separated easily from the reaction media and reused without any activity loss. In effect, the quality of the catalyst remained the same for eight cycles. The excellent performance of p(NaAMPS-co-AN)‐[Mn(TMPyP] is mostly attributed to its macroporous structure which allow for a rapid diffusion of the reactants to the reactive Mn(III) centers. High stability and reusability of catalyst without leaching is may be due to the AN. In fact, p(NaAMPS-co-AN)‐[Mn(TMPyP)] has chemical cross-linker, MBA, and physical cross-linker, AN. In a similar vein, the FT-IR spectra and atomic absorption spectroscopy confirmed the great recyclability, durability, and leaching resistance of the catalyst.

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Section: Synthesis and Characterizationmentioning

confidence: 96%

Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Reusable Manganese Porphyrin under Mild Aqueous Conditions

Sokhandan-Koirim

Ghorbanloo

Mokary-Yazdely

2022

Preprint

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“…In contrast, the photophysical properties of TMPyP encapsulated within two Cd-based MOFs (MOM-11 and MOM-12) fix the orientation of the porphyrin peripheral pyridinium groups relative to the porphyrin plane. 14 These fixed orientations have a significant effect on the porphyrin S 1 -CT coupled excited state leading to differences in steady state emission, emission lifetimes, and absorption properties. In addition, it is observed that the pores of CdTMPyP@MOM-11 and CdTMPyP@MOM-12 also restrict out of plane porphyrin ring distortions associated with sit-atop porphyrins resulting in extended triplet state lifetimes.…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11][12][13] With regards to metalloporphyrins, previous studies have reported on the photophysics of Zn(II) and Cd(II) metallated tetra (N-methyl-4-pyridyl)-21H,23H-porphine (TMPyP) Zn(II)tetramethyl pyridyl porphyrin (ZnTMPyP) encapsulated within the HKUST-1, MOM-11 and MOM-12 frameworks, respectively. 13,14 For ZnTMPyP, the lowest energy singlet excited state is a mixture of a charge transfer state (CT) (charge delocalization from the porphyrin ring to the cationic pyridinium rings) and a singlet π* (S 1 ) excited singlet state with the degree of mixing related to the rotational angle of the pyridinium group relative to the porphyrin plane. 15,16 With regards to ZnTMPyP@HKUST-1(Zn), the photophysical data are consistent with the ZnTMPyP being constrained within a an environment in which the peripheral pyridyl groups have restricted rotational motion and are nearly perpendicular with the porphyrin plane.…”

Section: Introductionmentioning

confidence: 99%

Photophysical comparison of Zn(ii) phthalocyanaine tetrasulfonate and Zn(ii) tetrakis(4-sulfonatophenyl)porphyrin encapsulated within the Zn-polyhedral metal organic framework, HKUST-1(Zn)

Larsen

Wojtas

2022

Dalton Trans.

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“…A typical example is that Larsen's group has successfully regulated the channel structure of Cd-MOFs through adding diversity auxiliary ligands. [10] Moreover, Hong-Cai Zhou groups use a multidentate flexible ligand HTDBD to synthesize mesoporous Cd-MOFs with extra-large channel size. [11] However, there are few reports on channel symmetry and internal environmental aspects.…”

Section: Introductionmentioning

confidence: 99%

Channel regulation through solvents for Cd‐MOFs based on p‐methoxyphenyl imidazole dicarboxylate: Synthesis, crystal structure, fluorescence, and explosive identification

Jiang

Dong

et al. 2021

J Chinese Chemical Soc

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Under different solvent systems, the reaction of Cd(NO 3 ) 2 Á4H 2 O with 2-pmethoxyphenyl-1H-imidazole-4,5-dicarboxylic acid (p-H 3 MOPhIDC) ligand produce two new Cd-MOFs, [Cd(p-HMOPhIDC)(C 2 H 5 OH)] n (1) and [Cd 2 (p-HMOPhIDC) 2 (Py)(C 2 H 5 OH)] n (2). Structural analysis shows that although the two Cd-MOFs have the same six-coordinated distorted octahedron geometry of the Cd(II) centers and the similar framework structure, they have different coordinated polymerization unit symmetry and internal environment in the channels. Among them, the polymerization unit in the channel of Cd-MOFs 1 is centrosymmetric, while the polymerization unit in the channel of Cd-MOFs 2 is asymmetric. Compared with the free p-H 3 MOPhIDC ligand, the fluorescence peaks of the two Cd-MOFs in the solid-state have undergone a slightly red shiftand enhancement. This is due to the increased rigidity of the ligand after the coordination of the metal ions with the ligand, which reduces the energy loss of thermal vibration. The fluorescence enhancement of Cd-MOFs 1 is greater than that of 2, which is related to the symmetry of the coordination polymerization units in the two Cd-MOFs channels. In addition, Cd-MOFs 2 can highly sensitive sense 2,4-dinitrotoluen (DNP) and 2,4,6-trinitrophenol (TNP) through luminescence quenching effect, whereas 1 cannot. This result is due to the difference in the environment within their channels.

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Pore modulation of guest photophysics in metal organic frameworks: Photophysical studies of meso-tetra (N-methyl-4-pyridyl) porphine encapsulated within MOM-11 and MOM-12

Cited by 13 publications

References 50 publications

Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Reusable Manganese Porphyrin under Mild Aqueous Conditions

Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Reusable Manganese Porphyrin under Mild Aqueous Conditions

Photophysical comparison of Zn(ii) phthalocyanaine tetrasulfonate and Zn(ii) tetrakis(4-sulfonatophenyl)porphyrin encapsulated within the Zn-polyhedral metal organic framework, HKUST-1(Zn)

Channel regulation through solvents for Cd‐MOFs based on p‐methoxyphenyl imidazole dicarboxylate: Synthesis, crystal structure, fluorescence, and explosive identification

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