Synthesis, structure, and cation complexation of a novel crown ether porphyrin

Liu, Yen-Chun; Kuo, Ming-Cheng; Lee, Cheng-Wei; Liang, You-Ren; Lee, Gene‐Hsiang; Peng, Shie‐Ming; Yeh, Chen‐Yu

doi:10.1016/j.tetlet.2008.10.014

Cited by 14 publications

(4 citation statements)

References 32 publications

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“…All compounds were optimized using the same methodology. Previous studies have shown that in the absence of a crown ether ring attached to the meso-site of the porphyrin ring, all atoms on the porphyrin ring are arranged in a planar configuration [29,[42][43][44][45]. The coordination of Fe(III) from FeCl 3 with the N atom in the porphyrin ring did not significantly affect the planar configuration of the porphyrin ring.…”

Section: Optimized Structure and Bonding Propertiesmentioning

confidence: 84%

“…The catalytic activity of FeTC 4 PCl and FeTPPCl complexes was evaluated for the oxidation of cyclohexene with O 2 following the literature procedure [28,29]. FeTC 4 PCl (2.0 mg, 0.00096 mmol) and cyclohexene (2.0 mL, 19.76 mmol) were added to a round bottom flask.…”

Section: Materials and Catalytic Property Studiesmentioning

confidence: 99%

Section: Optimized Structure and Bonding Propertiesmentioning

confidence: 99%

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Experimental and Theoretical Study on Crown Ether-Appended-Fe(III) Porphyrin Complexes and Catalytic Oxidation Cyclohexene with O2

Feng

et al. 2023

Molecules

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Modifying non-precious metal porphyrins at the meso-position is sufficient to further improve the ability to activate O2 and the selectivity of the corresponding redox products. In this study, a crown ether-appended Fe(III) porphyrin complex (FeTC4PCl) was formed by replacing Fe(III) porphyrin (FeTPPCl) at the meso-position. The reactions of FeTPPCl and FeTC4PCl catalysed by O2 oxidation of cyclohexene under different conditions were studied, and three main products, 2-cyclohexen-1-ol (1), 2-cyclohexen-1-one (2), and 7-oxabicyclo[4.1.0]heptane (3), were obtained. The effects of reaction temperature, reaction time, and the addition of axial coordination compounds on the reactions were investigated. The conversion of cyclohexene reached 94% at 70 °C after 12 h, and the selectivity toward product 1 was 73%. The geometrical structure optimization, molecular orbital energy level analysis, atomic charge, spin density, and density of orbital states analysis of FeTPPCl, FeTC4PCl, as well as the oxygenated complexes (Fe-O2)TCPPCl and (Fe-O2)TC4PCl formed after adsorption of O2, were carried out using the DFT method. The results of thermodynamic quantity variation with reaction temperature and Gibbs free energy variation were also analysed. Finally, based on experimental and theoretical analysis, the mechanism of the cyclohexene oxidation reaction with FeTC4PCl as a catalyst and O2 as an oxidant was deduced, and the reaction mechanism was obtained as a free radical chain reaction process.

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Section: Optimized Structure and Bonding Propertiesmentioning

confidence: 84%

Section: Materials and Catalytic Property Studiesmentioning

confidence: 99%

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Experimental and Theoretical Study on Crown Ether-Appended-Fe(III) Porphyrin Complexes and Catalytic Oxidation Cyclohexene with O2

Feng

et al. 2023

Molecules

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“…Intriguing supramolecular systems capable of electron transfer were developed by D'Souza, Ito and co-workers, showing selective multitopic receptors binding different alkali and transition metal cations with intramolecular photoinduced electron transfer [48,80]. Further applications of crown etherappended porphyrins acting as multitopic receptors, catalytically active species, and ligands were also investigated [81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99].…”

Section: Meso-crowned Porphyrinsmentioning

confidence: 99%

Tying a knot between crown ethers and porphyrins

Matviyishyn,

Szyszko

2023

Beilstein J. Org. Chem.

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Porphyrins and crown ether hybrids have emerged as a promising class of molecules composed of elements of a tetrapyrrole macrocycle and an oligo(ethylene glycol) segment. These hybrid systems constitute a broad group of compounds, including crowned porphyrins, crownphyrins, and calixpyrrole-crown ether systems forming Pacman complexes with transition metals. Their unique nature accustoms them as excellent ligands and hosts capable of binding guest molecules/ions, but also to undergo unusual transformations, such as metal-induced expansion/contraction. Depending on the design of the particular hybrid, they present unique features involving intriguing redox chemistry, interesting optical properties, and reactivity towards transition metals. In this perspective article, the overview of both the early designs of porphyrin-crown ether hybrids, as well as the most recent advances in the synthesis and characterisation of this remarkable group of macrocyclic systems, are addressed. The discussion covers the strategies employed in synthesising these systems, including cyclisation reactions, self-assembly, and their remarkable reactivity. The potential applications of porphyrin-crown ether hybrids are also highlighted. Moreover, the discussion identifies the challenges associated with synthesising and characterising hybrids, outlining the possible future directions.

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