Picosecond charge separation and triplet formation in a closely spaced photosynthetic model system

U. Hofstra; T. J. Schaafsma; G. M. Sanders; M. Van Dijk; H. C. Van Der Plas; D. G. Johnson; M. R. Wasielewski

doi:10.1016/0009-2614(88)80090-3

Picosecond charge separation and triplet formation in a closely spaced photosynthetic model system

U. Hofstra^*, T. J. Schaafsma, G. M. Sanders, M. Van Dijk, H. C. Van Der Plas, D. G. Johnson, M. R. Wasielewski

^*Corresponding author for this work

Chemistry

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

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Abstract

Intramolecular electron transfer has been investigated for three diphenyletioporphyrins covalently linked to an anthraquinone via a sulfonyloxy bridge at the ortho, meta or para substitution position of the phenyl groups of the porphyrin. The ortho-linked porphyrin is strongly folded and exhibits extremely fast charge separation (CS) and recombination (CR) between porphyrin and anthraquinone (k_CS > 3 × 10¹¹ s^-1 and k_CR = 5.9 × 10¹⁰ s^-1 in CH₂Cl₂). The less-folded meta- and para-linked porphyrins have smaller electron transfer rate constants. For the ortho-linked compound in toluene a biphasic charge separation is observed. The triplet state is formed in high yield via fast intersystem crossing in the charge-separated state.

Original language	English (US)
Pages (from-to)	169-175
Number of pages	7
Journal	Chemical Physics Letters
Volume	151
Issue number	1-2
DOIs	https://doi.org/10.1016/0009-2614(88)80090-3
State	Published - Oct 7 1988

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Picosecond charge separation and triplet formation in a closely spaced photosynthetic model system",

abstract = "Intramolecular electron transfer has been investigated for three diphenyletioporphyrins covalently linked to an anthraquinone via a sulfonyloxy bridge at the ortho, meta or para substitution position of the phenyl groups of the porphyrin. The ortho-linked porphyrin is strongly folded and exhibits extremely fast charge separation (CS) and recombination (CR) between porphyrin and anthraquinone (kCS > 3 × 1011 s-1 and kCR = 5.9 × 1010 s-1 in CH2Cl2). The less-folded meta- and para-linked porphyrins have smaller electron transfer rate constants. For the ortho-linked compound in toluene a biphasic charge separation is observed. The triplet state is formed in high yield via fast intersystem crossing in the charge-separated state.",

author = "U. Hofstra and Schaafsma, {T. J.} and Sanders, {G. M.} and {Van Dijk}, M. and {Van Der Plas}, {H. C.} and Johnson, {D. G.} and Wasielewski, {M. R.}",

note = "Funding Information: We thank Mr. B. van Veldhuizen for recordingt he NMR spectra,M r. A. van Hoek for the fluorescence lifetime measurementsa nd Mr. T.A. Roelyfs for mi-crosccondt ransient absorption measurementsT. his investigation was supportedb y the NetherlandsO r-ganization for Chemical Research (SON) with financial aid from the Netherlands Organization for the Advancement of Pure Research (ZWO). Work at Argonne National Laboratory was supportedb y the Division of Chemical Sciences,O ftice of Basic Energy Sciences, US Department of Energy under contract W-3 l-109-ENG-38.",

year = "1988",

month = oct,

day = "7",

doi = "10.1016/0009-2614(88)80090-3",

language = "English (US)",

volume = "151",

pages = "169--175",

journal = "Chemical Physics Letters",

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T1 - Picosecond charge separation and triplet formation in a closely spaced photosynthetic model system

AU - Hofstra, U.

AU - Schaafsma, T. J.

AU - Sanders, G. M.

AU - Van Dijk, M.

AU - Van Der Plas, H. C.

AU - Johnson, D. G.

AU - Wasielewski, M. R.

N1 - Funding Information: We thank Mr. B. van Veldhuizen for recordingt he NMR spectra,M r. A. van Hoek for the fluorescence lifetime measurementsa nd Mr. T.A. Roelyfs for mi-crosccondt ransient absorption measurementsT. his investigation was supportedb y the NetherlandsO r-ganization for Chemical Research (SON) with financial aid from the Netherlands Organization for the Advancement of Pure Research (ZWO). Work at Argonne National Laboratory was supportedb y the Division of Chemical Sciences,O ftice of Basic Energy Sciences, US Department of Energy under contract W-3 l-109-ENG-38.

PY - 1988/10/7

Y1 - 1988/10/7

N2 - Intramolecular electron transfer has been investigated for three diphenyletioporphyrins covalently linked to an anthraquinone via a sulfonyloxy bridge at the ortho, meta or para substitution position of the phenyl groups of the porphyrin. The ortho-linked porphyrin is strongly folded and exhibits extremely fast charge separation (CS) and recombination (CR) between porphyrin and anthraquinone (kCS > 3 × 1011 s-1 and kCR = 5.9 × 1010 s-1 in CH2Cl2). The less-folded meta- and para-linked porphyrins have smaller electron transfer rate constants. For the ortho-linked compound in toluene a biphasic charge separation is observed. The triplet state is formed in high yield via fast intersystem crossing in the charge-separated state.

AB - Intramolecular electron transfer has been investigated for three diphenyletioporphyrins covalently linked to an anthraquinone via a sulfonyloxy bridge at the ortho, meta or para substitution position of the phenyl groups of the porphyrin. The ortho-linked porphyrin is strongly folded and exhibits extremely fast charge separation (CS) and recombination (CR) between porphyrin and anthraquinone (kCS > 3 × 1011 s-1 and kCR = 5.9 × 1010 s-1 in CH2Cl2). The less-folded meta- and para-linked porphyrins have smaller electron transfer rate constants. For the ortho-linked compound in toluene a biphasic charge separation is observed. The triplet state is formed in high yield via fast intersystem crossing in the charge-separated state.

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Picosecond charge separation and triplet formation in a closely spaced photosynthetic model system

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