Vibrational properties of new corrole–fullerene dyad and its components

Lewandowska, Kornelia; Barszcz, Bolesław; Wolak, J.; Graja, A.; Grzybowski, Marek; Gryko, Daniel T.

doi:10.1016/j.dyepig.2012.07.024

Cited by 22 publications

(15 citation statements)

References 24 publications

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“…[2] Porphyrins have been commonlyu sed as photosensitizers for the construction of artificial photosynthetic systemsb ecause of their resemblance to the naturally occurring chlorophyll pigments. [3] However, other sensitizers, including phthalocyanines, [4] corroles, [5] subphthalocyanines, [6] bodipy, [7] and structural isomers of porphyrins [8] have also been exploited for this purpose. Furthermore, in recent work, molecular engineering has been applied in the preparation of elegant multi-modular donor-acceptor systems that are capable of wide-band capturea nd of generating the long sought after long-lived charge-separated states upon photoexcitation.…”

Section: Introductionmentioning

confidence: 99%

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Ngo

Zieba

Webre

et al. 2015

Chemistry A European J

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An electron-deficient copper(III) corrole was utilized for the construction of donor-acceptor conjugates with zinc(II) porphyrin (ZnP) as a singlet excited state electron donor, and the occurrence of photoinduced charge separation was demonstrated by using transient pump-probe spectroscopic techniques. In these conjugates, the number of copper corrole units was varied from 1 to 2 or 4 units while maintaining a single ZnP entity to observe the effect of corrole multiplicity in facilitating the charge-separation process. The conjugates and control compounds were electrochemically and spectroelectrochemically characterized. Computational studies revealed ground state geometries of the compounds and the electron-deficient nature of the copper(III) corrole. An energy level diagram was established to predict the photochemical events by using optical, emission, electrochemical, and computational data. The occurrence of charge separation from singlet excited zinc porphyrin and charge recombination to yield directly the ground state species were evident from the diagram. Femtosecond transient absorption spectroscopy studies provided spectral evidence of charge separation in the form of the zinc porphyrin radical cation and copper(II) corrole species as products. Rates of charge separation in the conjugates were found to be of the order of 10(10) s(-1) and increased with increasing multiplicity of copper(III) corrole entities. The present study demonstrates the importance of copper(III) corrole as an electron acceptor in building model photosynthetic systems.

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Section: Introductionmentioning

confidence: 99%

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Ngo

Zieba

Webre

et al. 2015

Chemistry A European J

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“…As a result, numerous porphyrin/fullerenes systems have been reported in the literature . Surprisingly, in spite of all of the positive features of corroles, the use of corroles in building corrole/fullerene donor–acceptor assemblies has been limited to only a handful of studies …”

Section: Introductionmentioning

confidence: 99%

Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C₆₀ and Triphenylamine–Corrole‐C₆₀ Donor–Acceptor Conjugates

Sudhakar

Gokulnath

Giribabu

et al. 2015

Chemistry An Asian Journal

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Closely positioned donor-acceptor pairs facilitate electron- and energy-transfer events, relevant to light energy conversion. Here, a triad system TPACor-C60 , possessing a free-base corrole as central unit that linked the energy donor triphenylamine (TPA) at the meso position and an electron acceptor fullerene (C60) at the β-pyrrole position was newly synthesized, as were the component dyads TPA-Cor and Cor-C60. Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady-state fluorescence studies showed efficient energy transfer from (1) TPA* to the corrole and subsequent electron transfer from (1) corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron-transfer products, the corrole radical cation (Cor(⋅+) in Cor-C60 and TPA-Cor(⋅+) in TPACor-C60) and fullerene radical anion (C60(⋅-)), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, kCS , was found to be about 10(11) s(-1), suggesting the occurrence of an ultrafast charge-separation process. Interestingly, although an order of magnitude slower than kCS , the rate of charge recombination, kCR , was also found to be rapid (kCR ≈10(10) s(-1)), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge-separated species relaxed directly to the ground state in polar solvents while in toluene, formation of (3) corrole* was observed, thus implying that the energy of the charge-separated state in a nonpolar solvent is higher than the energy of (3) corrole* being about 1.52 eV. That is, ultrafast formation of a high-energy charge-separated state in toluene has been achieved in these closely spaced corrole-fullerene donor-acceptor conjugates.

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“…The shift observed is direct evidence of the π–π interaction between the nanotube sidewall and the corrole ring in the nanocomposite dispersion . The resonant Raman features observed in the spectra for NO 2 –Cor–Co mainly arise from the pyrrole and phenyl units of the macrocycle (Figure and Table S2 in the Supporting Information) . Notably, in the nanocomposites, some small signals corresponding to the corrole molecule can be observed in the low‐frequency region (

\overset{ν}{true}

=380, 990, 1074, and 1234 cm −1 ).…”

Section: Resultsmentioning

confidence: 84%

“…[48] The resonant Raman features observed in the spectra for NO 2 -Cor-Co mainly arise from the pyrrole and phenyl units of the macrocycle ( Figure 5 and Ta ble S2 in the Supporting Information). [49][50][51] Notably,i n the nanocomposites, some small signals corresponding to the corrole molecule can be observed in the low-frequency region (ñ = 380,990, 1074, and 1234 cm À1 ).…”

Section: Co III -P-nitrophenylcorrole Adsorbedonc Arbon Nanotubesmentioning

confidence: 94%

Iron and Cobalt Corroles in Solution and on Carbon Nanotubes as Molecular Photocatalysts for Hydrogen Production by Water Reduction

et al. 2017

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Abstract:Here we report the use of cobalt and iron corrole complexes as catalysts of H2O reduction to generate H2. Electro and photocatalysis has been used in the case of dissolved corroles for water reduction with inspiring results. Carbon nanotubes doped with corroles were used as photo-electrochemical catalysts allowing getting very low overpotential values and increased hydrogen production, achieving incredibly high turnover numbers and turnover frequencies of ca. 10 7 and 10 5 , respectively. Through this last process we were able to obtain 1mmol of H2 by using minuscule amounts of catalyst, in the order of pictograms. The reactions can be carried out in water, without the need of organic solvents. Remarkably, the photoelectrochemical catalytic efficiency was increased by five orders of magnitude when adsorbing the molecular catalysts onto carbon nanotubes.

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Vibrational properties of new corrole–fullerene dyad and its components

Cited by 22 publications

References 24 publications

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C₆₀ and Triphenylamine–Corrole‐C₆₀ Donor–Acceptor Conjugates

Iron and Cobalt Corroles in Solution and on Carbon Nanotubes as Molecular Photocatalysts for Hydrogen Production by Water Reduction

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Vibrational properties of new corrole–fullerene dyad and its components

Cited by 22 publications

References 24 publications

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C60 and Triphenylamine–Corrole‐C60 Donor–Acceptor Conjugates

Iron and Cobalt Corroles in Solution and on Carbon Nanotubes as Molecular Photocatalysts for Hydrogen Production by Water Reduction

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Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C₆₀ and Triphenylamine–Corrole‐C₆₀ Donor–Acceptor Conjugates