Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays

Taeyeon Kim; Jinseok Kim; Hirotaka Mori; Seongchul Park; Manho Lim; Atsuhiro Osuka; Dongho Kim

doi:10.1039/c7cp01943b

Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays

Taeyeon Kim, Jinseok Kim, Hirotaka Mori, Seongchul Park, Manho Lim, Atsuhiro Osuka, Dongho Kim

Department of Chemistry

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

39 Citations (Scopus)

Abstract

Herein, we revealed a symmetry-breaking charge transfer (SBCT) process in the excited state of a directly linked push-pull porphyrin dyad (AD) and triad (ADA) via spectroscopic measurements including steady-state absorption and fluorescence, time-resolved fluorescence (TRF), femtosecond transient absorption (fs-TA), and time-resolved infrared (TRIR) measurements. Unprecedented broad fluorescence spectra were observed for porphyrin arrays in polar solvents; these were attributed to the existence of a charge transfer state as evidenced by the TRF measurements. TA measurements also revealed emerging features of a CT state for AD and ADA in polar solvents. These dynamics were also confirmed via TRIR measurements, which provided further information on the solvation and structural relaxation processes of the SBCT process. This is the first observation of an SBCT process in porphyrin arrays, providing fundamental understanding of the strongly coupled porphyrin arrays. Thus, the results of this study reveal the potential of the porphyrin arrays in relevant applications requiring SBCT.

Original language	English
Pages (from-to)	13970-13977
Number of pages	8
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	21
DOIs	https://doi.org/10.1039/c7cp01943b
Publication status	Published - 2017

Bibliographical note

Funding Information:
This research was conducted at the University of Yonsei and supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea (D. K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2015-C3-024). The work at Kyoto was supported by the JSPS KAKENHI Grant Numbers 25220802 and 25620031. H. M. acknowledges the JSPS Fellowship for Young Scientists. The work at Busan was supported by the National Research Foundation of Korea (NRF) with a grant funded by the Korea government (MEST) (NRF-2014R1A2A2A01002456, NRF-2014R1A4A1001690).

Publisher Copyright:
© the Owner Societies 2017.

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1039/c7cp01943b

Cite this

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title = "Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays",

abstract = "Herein, we revealed a symmetry-breaking charge transfer (SBCT) process in the excited state of a directly linked push-pull porphyrin dyad (AD) and triad (ADA) via spectroscopic measurements including steady-state absorption and fluorescence, time-resolved fluorescence (TRF), femtosecond transient absorption (fs-TA), and time-resolved infrared (TRIR) measurements. Unprecedented broad fluorescence spectra were observed for porphyrin arrays in polar solvents; these were attributed to the existence of a charge transfer state as evidenced by the TRF measurements. TA measurements also revealed emerging features of a CT state for AD and ADA in polar solvents. These dynamics were also confirmed via TRIR measurements, which provided further information on the solvation and structural relaxation processes of the SBCT process. This is the first observation of an SBCT process in porphyrin arrays, providing fundamental understanding of the strongly coupled porphyrin arrays. Thus, the results of this study reveal the potential of the porphyrin arrays in relevant applications requiring SBCT.",

author = "Taeyeon Kim and Jinseok Kim and Hirotaka Mori and Seongchul Park and Manho Lim and Atsuhiro Osuka and Dongho Kim",

note = "Funding Information: This research was conducted at the University of Yonsei and supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea (D. K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2015-C3-024). The work at Kyoto was supported by the JSPS KAKENHI Grant Numbers 25220802 and 25620031. H. M. acknowledges the JSPS Fellowship for Young Scientists. The work at Busan was supported by the National Research Foundation of Korea (NRF) with a grant funded by the Korea government (MEST) (NRF-2014R1A2A2A01002456, NRF-2014R1A4A1001690). Publisher Copyright: {\textcopyright} the Owner Societies 2017.",

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AU - Kim, Taeyeon

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AU - Lim, Manho

AU - Osuka, Atsuhiro

AU - Kim, Dongho

N1 - Funding Information: This research was conducted at the University of Yonsei and supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea (D. K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2015-C3-024). The work at Kyoto was supported by the JSPS KAKENHI Grant Numbers 25220802 and 25620031. H. M. acknowledges the JSPS Fellowship for Young Scientists. The work at Busan was supported by the National Research Foundation of Korea (NRF) with a grant funded by the Korea government (MEST) (NRF-2014R1A2A2A01002456, NRF-2014R1A4A1001690). Publisher Copyright: © the Owner Societies 2017.

PY - 2017

Y1 - 2017

N2 - Herein, we revealed a symmetry-breaking charge transfer (SBCT) process in the excited state of a directly linked push-pull porphyrin dyad (AD) and triad (ADA) via spectroscopic measurements including steady-state absorption and fluorescence, time-resolved fluorescence (TRF), femtosecond transient absorption (fs-TA), and time-resolved infrared (TRIR) measurements. Unprecedented broad fluorescence spectra were observed for porphyrin arrays in polar solvents; these were attributed to the existence of a charge transfer state as evidenced by the TRF measurements. TA measurements also revealed emerging features of a CT state for AD and ADA in polar solvents. These dynamics were also confirmed via TRIR measurements, which provided further information on the solvation and structural relaxation processes of the SBCT process. This is the first observation of an SBCT process in porphyrin arrays, providing fundamental understanding of the strongly coupled porphyrin arrays. Thus, the results of this study reveal the potential of the porphyrin arrays in relevant applications requiring SBCT.

AB - Herein, we revealed a symmetry-breaking charge transfer (SBCT) process in the excited state of a directly linked push-pull porphyrin dyad (AD) and triad (ADA) via spectroscopic measurements including steady-state absorption and fluorescence, time-resolved fluorescence (TRF), femtosecond transient absorption (fs-TA), and time-resolved infrared (TRIR) measurements. Unprecedented broad fluorescence spectra were observed for porphyrin arrays in polar solvents; these were attributed to the existence of a charge transfer state as evidenced by the TRF measurements. TA measurements also revealed emerging features of a CT state for AD and ADA in polar solvents. These dynamics were also confirmed via TRIR measurements, which provided further information on the solvation and structural relaxation processes of the SBCT process. This is the first observation of an SBCT process in porphyrin arrays, providing fundamental understanding of the strongly coupled porphyrin arrays. Thus, the results of this study reveal the potential of the porphyrin arrays in relevant applications requiring SBCT.

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Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays

Abstract

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