Propentdyopents and related compounds. Part 4. Propentdyopent–alkanol adducts by the photo-oxygenation of pyrromethenones

Bonnett, Raymond; Ioannou, Stella; Swanson, Fiona J.

doi:10.1039/p19890000711

Cited by 13 publications

(16 citation statements)

References 2 publications

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“…Materials and Methods: The propentdyopent methanol adduct was prepared as previously reported , . Acetonitrile (CH 3 CN), dichloromethane (CH 2 Cl 2 ), dimethylformamide (DMF), tetrahydrofuran (THF), and toluene were dried by passage through a solvent purifier.…”

Section: Methodsmentioning

confidence: 99%

“…We have shown that tetraethyl propentdyopent Hpdp coordinates divalent transition metals and that the resulting homoleptic pseudo‐tetrahedral complexes [M(pdp) 2 , Scheme ] host stable ligand‐based radicals upon one‐electron reduction . Although convenient syntheses of dipyrrindione ligands were first reported in the 1980s, their boron coordination has not been investigated to the best of our knowledge. Herein, we sought to combine the ability of the dipyrrindione moiety to act as a redox‐active ligand with the emission properties of BODIPY analogs to afford a novel redox‐switchable fluorophore.…”

Section: Introductionmentioning

confidence: 99%

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Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

2018

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The combination of reversible redox chemistry and bright redox‐responsive emission properties is key to the development of electrofluorochromic switches for applications in bioimaging and optoelectronics. Herein, the redox‐active dipyrrin‐1,9‐dione fragment, which is characteristic of the propentdyopent family of heme metabolites and urinary pigments, is employed for the synthesis of a BODIPY analog. This boron difluoride complex exhibits bright fluorescence in organic solvents and a significant ipsochromic shift to the cyan region when compared to typical green BODIPY dyes. Electrochemical and spectroscopic measurements show that the dipyrrindione ligand acts as an electron reservoir by hosting an unpaired spin upon one‐electron reduction. This ligand‐based redox event reversibly abolishes the fluorescence emission, thus switching off the novel electrofluorochromic system.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

2018

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“…An all-ethyl analog of the naturally occurring propentdyopents (which typically feature methyl, vinyl or propionate substituents) was prepared from the photo-oxygenation of tetraethyldipyrrinone (aka tetraethylpyrromethenone) and isolated as the methanol adduct HpdpÁMeOH as previously reported. 6,16,17 Propentdyopent complexes were prepared in good yields by briefly refluxing (10-30 min) methanolic solutions of HpdpÁMeOH in the presence of chloride or acetate salts of Co(II), Ni(II), Cu(II), and Zn(II) (see ESI † for experimental details). The progress of metal coordination was monitored by UV-visible absorption spectroscopy owing to the p-p* transitions in the visible region that are characteristic of dipyrrin complexes (Fig.…”

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confidence: 99%

Propentdyopent: the scaffold of a heme metabolite as an electron reservoir in transition metal complexes

et al. 2016

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“…EXPERIMENTAL Materials and methods. The tetraethyl dipyrrin-1,9-dione methanol adduct (Hpdp•MeOH) 70,97 and palladium(II) acetylacetonate (Pd(acac)2) 98 were prepared as previously reported. Dichloromethane (CH2Cl2), dimethylformamide (DMF), and pentane were dried by passage through a solvent purifier.…”

Section: Discussionmentioning

confidence: 99%

“…The tetraethyl dipyrrindione ligand was synthesized using previously reported methods 50,70 as a methanol adduct (Hpdp•MeOH, Chart 2a) and added to a dichloromethane solution of palladium(II) acetylacetonate. In these conditions, acidification of the reaction mixture was expected to facilitate the dissociation of the bidentate acacligands and their replacement with a higher-affinity ligand.…”

Section: Synthesis and Chemical Characterizationmentioning

confidence: 99%

Stabilization of a Triplet Diradical on a Binuclear palladium(II) Dipyrrindione

Cj¹,

Av²,

Conradie³

et al. 2021

Preprint

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Porphyrins and other macrocyclic oligopyrroles form a versatile class of redox-active ligands and electron reservoirs. The stabilization of unpaired electrons within oligopyrrolic π systems adds to the available reactivity pathways and spin states of metal complexes for applications in catalysis and functional materials. In this context, bidentate dipyrrindiones are emerging as compact platforms for one-electron redox chemistry in transition metal complexes. We report the synthesis of a bis(aqua) palladium(II) dipyrrindione complex and its deprotonation-driven dimerization to form a hydroxo-bridged dinuclear complex. Electrochemical, spectroelectrochemical, and computational analyses indicate the accessibility of two reduction processes on the dipyrrindione frameworks of the dinuclear complex. The product of a two-electron reduction by cobaltocene was isolated and characterized. In the solid state, this cobaltoceni- um salt features a folded dianionic complex maintaining the hydroxo bridges between the divalent palladium centers. X- band and Q-band EPR spectroscopic experiments and DFT computational analysis allow assignment of the dianionic species as a triplet diradical supported by the dipyrrindione ligands. These dipyrroles, which are also known as propentdyopents and were initially isolated as urinary pigments and heme metabolites, extend the rich chemistry of bidentate dipyrrin ligands to include the stabilization of ligand-centered radicals.

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Propentdyopents and related compounds. Part 4. Propentdyopent–alkanol adducts by the photo-oxygenation of pyrromethenones

Cited by 13 publications

References 2 publications

Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

Propentdyopent: the scaffold of a heme metabolite as an electron reservoir in transition metal complexes

Stabilization of a Triplet Diradical on a Binuclear palladium(II) Dipyrrindione

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