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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
Engaging copper (III) corrole as an electron acceptor: photoinduced charge separation in zinc porphyrin-copper corrole donor-acceptor conjugates
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 1010?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.
0947-6539
1301-1312
Ngo, Thien H.
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Zieba, David
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Webre, Whitney A.
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Lim, Gary N.
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Karr, Paul A.
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Kord, Scheghajegh
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Jin, Shangbin
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Ariga, Katsuhiko
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Galli, Marzia
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Goldup, Steve
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Hill, Jonathan P.
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D'Souza, Francis
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Ngo, Thien H.
a6697de9-4b83-4eeb-b516-e05b33cc437a
Zieba, David
6cd5e142-f59a-40da-9ba2-b5a681fa91e4
Webre, Whitney A.
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Lim, Gary N.
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Karr, Paul A.
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Kord, Scheghajegh
70cda9e7-0a75-4a2a-a404-2f9cd75f5633
Jin, Shangbin
e0a3cf64-6254-44b3-912b-a14160b1dd28
Ariga, Katsuhiko
d368003c-164f-4f22-a61e-919336ac87dd
Galli, Marzia
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Goldup, Steve
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Hill, Jonathan P.
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D'Souza, Francis
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Ngo, Thien H., Zieba, David, Webre, Whitney A., Lim, Gary N., Karr, Paul A., Kord, Scheghajegh, Jin, Shangbin, Ariga, Katsuhiko, Galli, Marzia, Goldup, Steve, Hill, Jonathan P. and D'Souza, Francis (2016) Engaging copper (III) corrole as an electron acceptor: photoinduced charge separation in zinc porphyrin-copper corrole donor-acceptor conjugates. Chemistry - A European Journal, 22 (4), 1301-1312. (doi:10.1002/chem.201503490).

Record type: Article

Abstract

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 1010?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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e-pub ahead of print date: 30 November 2015
Published date: 22 January 2016
Organisations: Chemistry

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Local EPrints ID: 391089
URI: http://eprints.soton.ac.uk/id/eprint/391089
ISSN: 0947-6539
PURE UUID: d3500bde-8b79-418a-b507-53b4d86b1267
ORCID for Steve Goldup: ORCID iD orcid.org/0000-0003-3781-0464

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Date deposited: 08 Apr 2016 08:54
Last modified: 17 Dec 2019 01:34

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Contributors

Author: Thien H. Ngo
Author: David Zieba
Author: Whitney A. Webre
Author: Gary N. Lim
Author: Paul A. Karr
Author: Scheghajegh Kord
Author: Shangbin Jin
Author: Katsuhiko Ariga
Author: Marzia Galli
Author: Steve Goldup ORCID iD
Author: Jonathan P. Hill
Author: Francis D'Souza

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