Supramolecular Self-Assembled Nanostructures Derived from Amplified Structural Isomerism of Zn(II)−Sn(IV)−Zn(II) Porphyrin Triads and Their Visible Light Photocatalytic Degradation of Pollutants †
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PROVIDER: S-EPMC11243107 | biostudies-literature | 2024 Jun
REPOSITORIES: biostudies-literature
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Project description:Three isomeric Zn(II)-Sn(IV)-Zn(II) porphyrin-based triads (T2, T3, and T4) were synthesized by the reaction of common Zn(II) porphyrins (ZnL) with different Sn(IV) porphyrins (SnP n ). The Sn(IV) porphyrin precursors differ with respect to the position of the pyridyl-N atoms. All compounds were characterized by 1H NMR, UV-vis, fluorescence spectroscopy, electrospray ionization-mass spectrometry, and field-emission scanning electron microscopy measurements. In these structures, the intramolecular cooperative metal-ligand coordination of the 3-pyridyl nitrogen in SnP 3 with axial ZnL and the π-π interactions between the adjacent porphyrin triad are the determining factors affecting the nanostructures of T3. Owing to the geometrical constraints of the SnP 2 center, this type of interaction is not possible for T2. Therefore, only the π-π interactions affect the self-assembly process. In the case of SnP 4 , intermolecular coordinative interactions and then π-π interactions are responsible for the nanostructure of T4. The morphology-dependent photocatalytic degradation of methyl orange (MO) dye in aqueous solution under visible light irradiation was observed for these photocatalysts, and the degradation ratio of MO varied from 76 to 94% within 100 min. Nanorod-shaped T3 exhibited higher performance compared to nanosphere T2 and nanoflake T4.
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Project description:Two robust Sn(IV)-porphyrin-based supramolecular arrays (1 and 2) were synthesized via the reaction of trans-Pd(PhCN)2Cl2 with two precursor building blocks (SnP1 and SnP2). The structural patterns in these architectures vary from 2D to 3D depending on the axial ligation of Sn(IV)-porphyrin units. A discrete 2D tetrameric supramolecule (1) was constructed by coordination of {(trans-dihydroxo)[5,10-bis(4-pyridyl)-15,20-bis(phenyl) porphyrinato]}tin(IV) (SnP1) with trans-PdCl2 units. In contrast, the coordination between the {(trans-diisonicotinato)[5,10-bis(4-pyridyl)-15,20-bis(phenyl)porphyrinato]}tin(IV) (SnP2) and trans-PdCl2 units formed a divergent 3D array (2). Axial ligation of the Sn(IV)-porphyrin building blocks not only alters the supramolecular arrays but also significantly modifies the nanostructures, including porosity, surface area, stability, and morphology. These structural changes consequently affected the photocatalytic degradation efficiency under visible-light irradiation towards acid orange 7 (AO) dye in an aqueous solution. The degradation efficiency of the AO dye in the aqueous solution was observed to be between 86% to 91% within 90 min by these photocatalysts.
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Project description:Nature routinely uses cooperative interactions to regulate cellular activity. For years, chemists have designed synthetic systems that aim toward harnessing the reactivity common to natural biological systems. By learning how to control these interactions in situ, one begins to allow for the preparation of man-made biomimetic systems that can efficiently mimic the interactions found in Nature. To this end, we have designed a synthetic protocol for the preparation of flexible metal-directed supramolecular cofacial porphyrin complexes which are readily obtained in greater than 90% yield through the use of new hemilabile porphyrin ligands with bifunctional ether-phosphine or thioether-phosphine substituents at the 5 and 15 positions on the porphyrin ring. The resulting architectures contain two hemilabile ligand-metal domains (RhI or CuI sites) and two cofacially aligned porphyrins (ZnII sites), offering orthogonal functionalities and allowing these multimetallic complexes to exist in two states, "condensed" or "open". Combining the ether-phosphine ligand with the appropriate RhI or CuI transition-metal precursors results in "open" macrocyclic products. In contrast, reacting the thioether-phosphine ligand with RhI or CuI precursors yields condensed structures that can be converted into their "open" macrocyclic forms via introduction of additional ancillary ligands. The change in cavity size that occurs allows these structures to function as allosteric catalysts for the acyl transfer reaction between X-pyridylcarbinol (where X = 2, 3, or 4) and 1-acetylimidazole. For 3- and 4-pyridylcarbinol, the "open" macrocycle accelerates the acyl transfer reaction more than the condensed analogue and significantly more than the porphyrin monomer. In contrast, an allosteric effect was not observed for 2-pyridylcarbinol, which is expected to be a weaker binder and is unfavorably constrained inside the macrocyclic cavity.
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