Synthesis of Porphyrin–Fullerene Dyads and Their Spectroscopic Properties

Leupold, S.; Shokati, Touraj; Eberle, Christoph; Borrmann, Tobias; Montforts, Franz‐Peter

doi:10.1002/ejoc.200800054

Cited by 9 publications

(2 citation statements)

References 32 publications

(10 reference statements)

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“…This reaction involves 1,3-dipolar cycloaddition of an azomethine ylide generated in situ with C 60 , and produced 1 in 19% yield. The product could in principle be a mixture of diastereomers due to the presence of two stereocenters on the pyrrolidine, − but NMR and thin layer chromatography indicated that only one isomer was present (as a pair of enantiomers). This is consistent with a concerted reaction of the azomethine ylide with C 60 …”

Section: Resultsmentioning

confidence: 99%

Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

et al. 2016

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In order to investigate the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C60) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CyP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CyP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of (1)P-C60-CyP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CyP. The P(•+)-C60(•-)-CyP charge-separated state transfers an electron to CyP to produce a final P(•+)-C60-CyP(•-) state. The same state is formed from P-C60-(1)CyP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediate P(•+)-C60(•-)-CyP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. This is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.

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Section: Resultsmentioning

confidence: 99%

Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

et al. 2016

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“…Fullerene (C 60 ) can be easily ligated to these dyes by cycloaddition reactions. Several dye‐fullerene conjugates, so called dyads, have been synthesized in the past years . The dyads have been constructed and investigated with the purpose to mimic natural photosynthesis and to understand fundamentals of photoinduced electron and energy transfer processes …”

Section: Introductionmentioning

confidence: 99%

Electron Transfer and Electron Excitation Processes in 2,5‐Diaminoterephthalate Derivatives with Broad Scope for Functionalization

et al. 2019

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Derivatives of 2,5‐diaminoterephthalate (DAT) are efficient fluorescence dyes that are also redox‐active, thus allowing for the electrochemical manipulation of spectral properties. The electrochemical behaviour of seven DAT derivatives was studied by cyclic voltammetry in dichloromethane. In the absence of a proton donor, DATs should be oxidized in two one‐electron steps. The first step is usually quasi‐reversible while the second step is either quasi‐reversible or irreversible. Some electrochemical properties such as the formal potentials and the ratio between the anodic and the cathodic current were determined from the cyclic voltammograms. Correlation between the formal potential of first oxidation and the absorption or the fluorescence emission wavelengths are established for this specific type of dyes. These correlations were confirmed with density functional theory calculations.

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A Dipyrrin Programmed for Covalent Loading with Fullerenes

Wurst

Kräutler

2018

Chemistry A European J

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We describe here a di‐(β,β′‐sulfoleno)pyrrin programmed for efficient and specific β,β′‐functionalization via [4+2] cycloaddition reactions. At 120 °C and in the presence of an excess of C60‐fullerene the di‐(β,β′‐sulfoleno)pyrrin decomposed cleanly, furnishing a di‐(β,β′‐fullereno)pyrrin and the corresponding monofullereno‐dipyrrin in an overall yield of 96 %. Hence, relatively mild thermolysis of the di‐(β,β′‐sulfoleno)pyrrin induced stepwise extrusion of two equivalents of SO2, producing highly reactive dipyrrin‐β,β′‐diene intermediates readily, providing a very effective path to [4+2]‐cycloadducts. As presented here by the example of the covalent attachment of C60‐fullerene units, a convenient general methodology for the efficient synthesis of covalent dipyrrin β,β′‐cycloadducts is made available.

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Synthesis of Porphyrin–Fullerene Dyads and Their Spectroscopic Properties

Abstract: Porphyrin-fullerene dyads with different linkages between the two subunits were synthesized for mimicking photosynthesis. NMR spectra and quantum mechanical calculations show special structural features that should influence lightinduced electron transfer of the photosynthetic process.

Cited by 9 publications

References 32 publications

Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator

Electron Transfer and Electron Excitation Processes in 2,5‐Diaminoterephthalate Derivatives with Broad Scope for Functionalization

A Dipyrrin Programmed for Covalent Loading with Fullerenes

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