Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer

Eduard Fron; Ania Deres; Susana Rocha; Gang Zhou; Klaus Müllen; Frans C. De Schryver; Michel Sliwa; Hiroshi Uji-i; Johan Hofkens; Tom Vosch

doi:10.1021/jp909295h

Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer

Eduard Fron, Ania Deres, Susana Rocha, Gang Zhou, Klaus Müllen, Frans C. De Schryver, Michel Sliwa, Hiroshi Uji-i, Johan Hofkens, Tom Vosch

17 Citations (Scopus)

Abstract

Insight into the exciton dynamics occurring in a polyfluorene- perylenediimide (PF-PDI) copolymer with a reaction mixture ratio of 100 fluorene units to 1 N,N′-bis(phenyl)-1,6,7,12-tetra(p-fert-octylphenoxy)- perylene3,4,9,10-tetracarboxylic acid diimide (PDI) is presented here. Time-correlated single photon counting and femtosecond transient absorption spectroscopy measurements on the PF-PDI copolymer have been employed to investigate the excited-state properties of the polyfluorene subunit where the exciton is localized (PF) and the incorporated PDI chromophore. The experimental results were compared with those obtained from a polyfluorene polymer (model PF) and a N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(p-fert- octylphenoxy)perylene-3,4,9,10-tetracarboxylic acid diimide (model PDI) which were used as reference compounds. Because of the high polydispersity of the PF-PDI copolymer, there is a polymer fraction present that contains no PDI chromophores (polyfluorene polymer fraction (PF polymer fraction)) and wide-field imaging of single polymers chains of the synthesized PF-PDI copolymer was used to estimate this PF polymer fraction. Following the primary excitation of the PF in the PF-PDI copolymer, energy hopping between PF's can occur. A fraction of the energy of the absorbed photons will be transferred to a PDI chromophore via energy transfer from a PF. In a polar solvent, a charge transfer state having the Si of the PDI moiety as a precursor state is found to form with high efficiency on a nanosecond time scale. The data suggest that a fraction of the absorbed energy is directed, transferred and used in charge separation, providing a clear view of a multistep mechanism of exciton dissociation into charges.

Original language	English
Journal	Journal of Physical Chemistry B
Volume	114
Issue number	3
Pages (from-to)	1277-1286
Number of pages	10
ISSN	1520-6106
DOIs	https://doi.org/10.1021/jp909295h
Publication status	Published - 28 Jan 2010

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http://pubs.acs.org/doi/full/10.1021/jp909295h

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@article{a1501318f99e42acae7a502d408afa17,

title = "Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer",

abstract = "Insight into the exciton dynamics occurring in a polyfluorene- perylenediimide (PF-PDI) copolymer with a reaction mixture ratio of 100 fluorene units to 1 N,N′-bis(phenyl)-1,6,7,12-tetra(p-fert-octylphenoxy)- perylene3,4,9,10-tetracarboxylic acid diimide (PDI) is presented here. Time-correlated single photon counting and femtosecond transient absorption spectroscopy measurements on the PF-PDI copolymer have been employed to investigate the excited-state properties of the polyfluorene subunit where the exciton is localized (PF) and the incorporated PDI chromophore. The experimental results were compared with those obtained from a polyfluorene polymer (model PF) and a N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(p-fert- octylphenoxy)perylene-3,4,9,10-tetracarboxylic acid diimide (model PDI) which were used as reference compounds. Because of the high polydispersity of the PF-PDI copolymer, there is a polymer fraction present that contains no PDI chromophores (polyfluorene polymer fraction (PF polymer fraction)) and wide-field imaging of single polymers chains of the synthesized PF-PDI copolymer was used to estimate this PF polymer fraction. Following the primary excitation of the PF in the PF-PDI copolymer, energy hopping between PF's can occur. A fraction of the energy of the absorbed photons will be transferred to a PDI chromophore via energy transfer from a PF. In a polar solvent, a charge transfer state having the Si of the PDI moiety as a precursor state is found to form with high efficiency on a nanosecond time scale. The data suggest that a fraction of the absorbed energy is directed, transferred and used in charge separation, providing a clear view of a multistep mechanism of exciton dissociation into charges.",

author = "Eduard Fron and Ania Deres and Susana Rocha and Gang Zhou and Klaus M{\"u}llen and {De Schryver}, {Frans C.} and Michel Sliwa and Hiroshi Uji-i and Johan Hofkens and Tom Vosch",

year = "2010",

month = jan,

day = "28",

doi = "10.1021/jp909295h",

language = "English",

volume = "114",

pages = "1277--1286",

journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical",

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TY - JOUR

T1 - Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer

AU - Fron, Eduard

AU - Deres, Ania

AU - Rocha, Susana

AU - Zhou, Gang

AU - Müllen, Klaus

AU - De Schryver, Frans C.

AU - Sliwa, Michel

AU - Uji-i, Hiroshi

AU - Hofkens, Johan

AU - Vosch, Tom

PY - 2010/1/28

Y1 - 2010/1/28

N2 - Insight into the exciton dynamics occurring in a polyfluorene- perylenediimide (PF-PDI) copolymer with a reaction mixture ratio of 100 fluorene units to 1 N,N′-bis(phenyl)-1,6,7,12-tetra(p-fert-octylphenoxy)- perylene3,4,9,10-tetracarboxylic acid diimide (PDI) is presented here. Time-correlated single photon counting and femtosecond transient absorption spectroscopy measurements on the PF-PDI copolymer have been employed to investigate the excited-state properties of the polyfluorene subunit where the exciton is localized (PF) and the incorporated PDI chromophore. The experimental results were compared with those obtained from a polyfluorene polymer (model PF) and a N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(p-fert- octylphenoxy)perylene-3,4,9,10-tetracarboxylic acid diimide (model PDI) which were used as reference compounds. Because of the high polydispersity of the PF-PDI copolymer, there is a polymer fraction present that contains no PDI chromophores (polyfluorene polymer fraction (PF polymer fraction)) and wide-field imaging of single polymers chains of the synthesized PF-PDI copolymer was used to estimate this PF polymer fraction. Following the primary excitation of the PF in the PF-PDI copolymer, energy hopping between PF's can occur. A fraction of the energy of the absorbed photons will be transferred to a PDI chromophore via energy transfer from a PF. In a polar solvent, a charge transfer state having the Si of the PDI moiety as a precursor state is found to form with high efficiency on a nanosecond time scale. The data suggest that a fraction of the absorbed energy is directed, transferred and used in charge separation, providing a clear view of a multistep mechanism of exciton dissociation into charges.

AB - Insight into the exciton dynamics occurring in a polyfluorene- perylenediimide (PF-PDI) copolymer with a reaction mixture ratio of 100 fluorene units to 1 N,N′-bis(phenyl)-1,6,7,12-tetra(p-fert-octylphenoxy)- perylene3,4,9,10-tetracarboxylic acid diimide (PDI) is presented here. Time-correlated single photon counting and femtosecond transient absorption spectroscopy measurements on the PF-PDI copolymer have been employed to investigate the excited-state properties of the polyfluorene subunit where the exciton is localized (PF) and the incorporated PDI chromophore. The experimental results were compared with those obtained from a polyfluorene polymer (model PF) and a N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(p-fert- octylphenoxy)perylene-3,4,9,10-tetracarboxylic acid diimide (model PDI) which were used as reference compounds. Because of the high polydispersity of the PF-PDI copolymer, there is a polymer fraction present that contains no PDI chromophores (polyfluorene polymer fraction (PF polymer fraction)) and wide-field imaging of single polymers chains of the synthesized PF-PDI copolymer was used to estimate this PF polymer fraction. Following the primary excitation of the PF in the PF-PDI copolymer, energy hopping between PF's can occur. A fraction of the energy of the absorbed photons will be transferred to a PDI chromophore via energy transfer from a PF. In a polar solvent, a charge transfer state having the Si of the PDI moiety as a precursor state is found to form with high efficiency on a nanosecond time scale. The data suggest that a fraction of the absorbed energy is directed, transferred and used in charge separation, providing a clear view of a multistep mechanism of exciton dissociation into charges.

U2 - 10.1021/jp909295h

DO - 10.1021/jp909295h

M3 - Journal article

C2 - 20050587

SN - 1520-6106

VL - 114

SP - 1277

EP - 1286

JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

IS - 3

ER -

Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer

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