Photoinduced energy and electron transfer in phenylethynyl-bridged zinc porphyrin-oligothienylenevinylene-C 60 ensembles

Maxence Urbani; Kei Ohkubo; D. M.Shafiqul Islam; Shunichi Fukuzumi; Fernando Langa

doi:10.1002/chem.201102260

Photoinduced energy and electron transfer in phenylethynyl-bridged zinc porphyrin-oligothienylenevinylene-C ₆₀ ensembles

Maxence Urbani, Kei Ohkubo, D. M.Shafiqul Islam, Shunichi Fukuzumi, Fernando Langa

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

Donor-bridge-acceptor triad (Por-2TV-C ₆₀) and tetrad molecules ((Por) ₂-2TV-C ₆₀), which incorporated C ₆₀ and one or two porphyrin molecules that were covalently linked through a phenylethynyl-oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto- and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C ₆₀ moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C ₆₀ moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C ₆₀. Then, back-electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)-2TV-C ₆₀ and (Por) ₂-2TV-C ₆₀ acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C ₆₀.

Original language	English
Pages (from-to)	7473-7485
Number of pages	13
Journal	Chemistry - A European Journal
Volume	18
Issue number	24
DOIs	https://doi.org/10.1002/chem.201102260
State	Published - 11 Jun 2012

Bibliographical note

Funding Information:
I would like to thank R. L. Cifelli, N. J Czaplewski, L. Vitt, G. Schnell, and C. Harper for helpful comments and discussion on this project. M. Caldwell, D. Winkler, and an anonymous reviewer provided useful comments on an earlier manuscript, which substantially improved this work. S. Madsen prepared the type specimen and C. McCallister prepared Figure 1. My gratitude also goes to all the personnel at KU, UALVP, and UMMZ for their assistance during my use of their collections. Financial support was provided by the American Federation of Mineralogical Societies, Dinamation International Society (Ying Chang Scholarship) Sigma Xi, the Graduate Student Sen- ate of the University of Oklahoma, the Department of Zoology of the University of Oklahoma as well as by National Geo-graphic Society Grants 4762-91 and 5021-92 and National Science Foundation grant DEB 9401094 to R. L. Cifelli.

Keywords

electron transfer
energy transfer
fullerenes
oligothienylenevinylene
porphyrins
zinc

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10.1002/chem.201102260

Cite this

@article{e717532a47744914937dd4c658288822,

title = "Photoinduced energy and electron transfer in phenylethynyl-bridged zinc porphyrin-oligothienylenevinylene-C 60 ensembles",

abstract = "Donor-bridge-acceptor triad (Por-2TV-C 60) and tetrad molecules ((Por) 2-2TV-C 60), which incorporated C 60 and one or two porphyrin molecules that were covalently linked through a phenylethynyl-oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto- and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C 60 moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C 60 moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C 60. Then, back-electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)-2TV-C 60 and (Por) 2-2TV-C 60 acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C 60.",

keywords = "electron transfer, energy transfer, fullerenes, oligothienylenevinylene, porphyrins, zinc",

author = "Maxence Urbani and Kei Ohkubo and Islam, {D. M.Shafiqul} and Shunichi Fukuzumi and Fernando Langa",

note = "Funding Information: I would like to thank R. L. Cifelli, N. J Czaplewski, L. Vitt, G. Schnell, and C. Harper for helpful comments and discussion on this project. M. Caldwell, D. Winkler, and an anonymous reviewer provided useful comments on an earlier manuscript, which substantially improved this work. S. Madsen prepared the type specimen and C. McCallister prepared Figure 1. My gratitude also goes to all the personnel at KU, UALVP, and UMMZ for their assistance during my use of their collections. Financial support was provided by the American Federation of Mineralogical Societies, Dinamation International Society (Ying Chang Scholarship) Sigma Xi, the Graduate Student Sen- ate of the University of Oklahoma, the Department of Zoology of the University of Oklahoma as well as by National Geo-graphic Society Grants 4762-91 and 5021-92 and National Science Foundation grant DEB 9401094 to R. L. Cifelli.",

year = "2012",

month = jun,

day = "11",

doi = "10.1002/chem.201102260",

language = "English",

volume = "18",

pages = "7473--7485",

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T1 - Photoinduced energy and electron transfer in phenylethynyl-bridged zinc porphyrin-oligothienylenevinylene-C 60 ensembles

AU - Urbani, Maxence

AU - Ohkubo, Kei

AU - Islam, D. M.Shafiqul

AU - Fukuzumi, Shunichi

AU - Langa, Fernando

N1 - Funding Information: I would like to thank R. L. Cifelli, N. J Czaplewski, L. Vitt, G. Schnell, and C. Harper for helpful comments and discussion on this project. M. Caldwell, D. Winkler, and an anonymous reviewer provided useful comments on an earlier manuscript, which substantially improved this work. S. Madsen prepared the type specimen and C. McCallister prepared Figure 1. My gratitude also goes to all the personnel at KU, UALVP, and UMMZ for their assistance during my use of their collections. Financial support was provided by the American Federation of Mineralogical Societies, Dinamation International Society (Ying Chang Scholarship) Sigma Xi, the Graduate Student Sen- ate of the University of Oklahoma, the Department of Zoology of the University of Oklahoma as well as by National Geo-graphic Society Grants 4762-91 and 5021-92 and National Science Foundation grant DEB 9401094 to R. L. Cifelli.

PY - 2012/6/11

Y1 - 2012/6/11

N2 - Donor-bridge-acceptor triad (Por-2TV-C 60) and tetrad molecules ((Por) 2-2TV-C 60), which incorporated C 60 and one or two porphyrin molecules that were covalently linked through a phenylethynyl-oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto- and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C 60 moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C 60 moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C 60. Then, back-electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)-2TV-C 60 and (Por) 2-2TV-C 60 acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C 60.

AB - Donor-bridge-acceptor triad (Por-2TV-C 60) and tetrad molecules ((Por) 2-2TV-C 60), which incorporated C 60 and one or two porphyrin molecules that were covalently linked through a phenylethynyl-oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto- and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C 60 moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C 60 moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C 60. Then, back-electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)-2TV-C 60 and (Por) 2-2TV-C 60 acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C 60.

KW - electron transfer

KW - energy transfer

KW - fullerenes

KW - oligothienylenevinylene

KW - porphyrins

KW - zinc

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