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

Research output: Contribution to journalArticle

10 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 languageEnglish
Pages (from-to)13970-13977
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume19
Issue number21
DOIs
Publication statusPublished - 2017 Jan 1

Fingerprint

Porphyrins
Crystal symmetry
Excited states
porphyrins
Charge transfer
broken symmetry
charge transfer
Fluorescence
fluorescence
excitation
Infrared radiation
Structural relaxation
Solvation
Relaxation processes
solvation
emerging

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Kim, Taeyeon ; Kim, Jinseok ; Mori, Hirotaka ; Park, Seongchul ; Lim, Manho ; Osuka, Atsuhiro ; Kim, Dongho. / Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays. In: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, No. 21. pp. 13970-13977.
@article{74056de4f04e4f45b8a85bcb777d9fda,
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",
year = "2017",
month = "1",
day = "1",
doi = "10.1039/c7cp01943b",
language = "English",
volume = "19",
pages = "13970--13977",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "21",

}

Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays. / Kim, Taeyeon; Kim, Jinseok; Mori, Hirotaka; Park, Seongchul; Lim, Manho; Osuka, Atsuhiro; Kim, Dongho.

In: Physical Chemistry Chemical Physics, Vol. 19, No. 21, 01.01.2017, p. 13970-13977.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Symmetry-breaking charge transfer in the excited state of directly linked push-pull porphyrin arrays

AU - Kim, Taeyeon

AU - Kim, Jinseok

AU - Mori, Hirotaka

AU - Park, Seongchul

AU - Lim, Manho

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2017/1/1

Y1 - 2017/1/1

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.

UR - http://www.scopus.com/inward/record.url?scp=85024363570&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85024363570&partnerID=8YFLogxK

U2 - 10.1039/c7cp01943b

DO - 10.1039/c7cp01943b

M3 - Article

AN - SCOPUS:85024363570

VL - 19

SP - 13970

EP - 13977

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 21

ER -