Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins

Hyun Sun Cho, Dae Hong Jeong, Min Chul Yoon, Yong Hee Kim, Yong Rok Kim, Dongho Kim, Sae Chae Jeoung, Seong Keun Kim, Naoki Aratani, Hideyuki Shinmori, Atsuhiro Osuka

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Abstract

The photoinduced energy transfer processes in 1,4-phenylene-, 1,3-phenylene, 1,2-phenylene, and 4,4′-biphenylene-linked and directly-linked Zn(II)-free base porphyrin heterodimers in THF were investigated by femtosecond transient absorption spectroscopy. The energy transfer rates were compared between TPP-type and OEP-type heterodimers respectively as A2u-HOMO and A]U-HOMO subunits, for evaluating the relative contribution of the through-bond and through-space interactions. The rate difference becomes smaller with a decrease of spacer, more than 10 for 1,4-bis(phenylethynyl)phenylene and 1,4-diphenylethynylene, 4 for 4,4′-biphenylene-linked heterodimer, and 3 for 1,3- and 1,4-phenylene-linked spacers. In the meso-meso directlylinked case, the energy transfer rates are the same ((0.55 ps)-1) for 5,5,15,15-tetrakis(3,5-bis(octyloxy)phenyl)-substituted and 5,5,15,15-tetrakis(pentafluorophenyl)-substituted heterodimers, featuring only a minor influence of the frontier orbital characteristics on the energy transfer rate. The energy transfer rates are identical (0.55 ps)-1 for the directly-linked meso-meso heterodimers substituted with 3,5-bis(octyloxy)phenyl and pentafluorophenyl groups regardless of the difference in the HOMO orbital symmetry characteristics, suggesting the predominant Coulombic interaction for the energy transfer in these close proximity porphyrin dimers. In the case of 1,2-phenylene-linked heterodimers, the choice of the peripheral substituents can lead to a state-to-state rapid energy transfer with a rate of (0.55 ps-1) for the TPP-type model or a delocalized excimer-like diporphyrin excited state for the OEP-type model. Collectively, these results indicate that even for the covalently-linked models the relative contribution of the through-space Coulombic interaction becomes increasingly important upon the decrease of the center-to-center separation. Especially, the fast and efficient energy transfer occurring in the directly-linked heterodimer illustrates that this porphyrin unit can be utilized as a good candidate for energy transfer functional arrays in molecular photonic devices.

Original languageEnglish
Pages (from-to)4200-4210
Number of pages11
JournalJournal of Physical Chemistry A
Volume105
Issue number17
Publication statusPublished - 2001 May 3

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Excited states
Energy transfer
Zinc
zinc
energy transfer
excitation
Porphyrins
porphyrins
spacers
orbitals
Photonic devices
interactions
excimers
Absorption spectroscopy
Dimers
proximity
absorption spectroscopy
dimers
photonics
symmetry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Sun Cho, Hyun ; Jeong, Dae Hong ; Yoon, Min Chul ; Kim, Yong Hee ; Kim, Yong Rok ; Kim, Dongho ; Jeoung, Sae Chae ; Kim, Seong Keun ; Aratani, Naoki ; Shinmori, Hideyuki ; Osuka, Atsuhiro. / Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins. In: Journal of Physical Chemistry A. 2001 ; Vol. 105, No. 17. pp. 4200-4210.
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title = "Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins",
abstract = "The photoinduced energy transfer processes in 1,4-phenylene-, 1,3-phenylene, 1,2-phenylene, and 4,4′-biphenylene-linked and directly-linked Zn(II)-free base porphyrin heterodimers in THF were investigated by femtosecond transient absorption spectroscopy. The energy transfer rates were compared between TPP-type and OEP-type heterodimers respectively as A2u-HOMO and A]U-HOMO subunits, for evaluating the relative contribution of the through-bond and through-space interactions. The rate difference becomes smaller with a decrease of spacer, more than 10 for 1,4-bis(phenylethynyl)phenylene and 1,4-diphenylethynylene, 4 for 4,4′-biphenylene-linked heterodimer, and 3 for 1,3- and 1,4-phenylene-linked spacers. In the meso-meso directlylinked case, the energy transfer rates are the same ((0.55 ps)-1) for 5,5,15,15-tetrakis(3,5-bis(octyloxy)phenyl)-substituted and 5,5,15,15-tetrakis(pentafluorophenyl)-substituted heterodimers, featuring only a minor influence of the frontier orbital characteristics on the energy transfer rate. The energy transfer rates are identical (0.55 ps)-1 for the directly-linked meso-meso heterodimers substituted with 3,5-bis(octyloxy)phenyl and pentafluorophenyl groups regardless of the difference in the HOMO orbital symmetry characteristics, suggesting the predominant Coulombic interaction for the energy transfer in these close proximity porphyrin dimers. In the case of 1,2-phenylene-linked heterodimers, the choice of the peripheral substituents can lead to a state-to-state rapid energy transfer with a rate of (0.55 ps-1) for the TPP-type model or a delocalized excimer-like diporphyrin excited state for the OEP-type model. Collectively, these results indicate that even for the covalently-linked models the relative contribution of the through-space Coulombic interaction becomes increasingly important upon the decrease of the center-to-center separation. Especially, the fast and efficient energy transfer occurring in the directly-linked heterodimer illustrates that this porphyrin unit can be utilized as a good candidate for energy transfer functional arrays in molecular photonic devices.",
author = "{Sun Cho}, Hyun and Jeong, {Dae Hong} and Yoon, {Min Chul} and Kim, {Yong Hee} and Kim, {Yong Rok} and Dongho Kim and Jeoung, {Sae Chae} and Kim, {Seong Keun} and Naoki Aratani and Hideyuki Shinmori and Atsuhiro Osuka",
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Sun Cho, H, Jeong, DH, Yoon, MC, Kim, YH, Kim, YR, Kim, D, Jeoung, SC, Kim, SK, Aratani, N, Shinmori, H & Osuka, A 2001, 'Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins', Journal of Physical Chemistry A, vol. 105, no. 17, pp. 4200-4210.

Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins. / Sun Cho, Hyun; Jeong, Dae Hong; Yoon, Min Chul; Kim, Yong Hee; Kim, Yong Rok; Kim, Dongho; Jeoung, Sae Chae; Kim, Seong Keun; Aratani, Naoki; Shinmori, Hideyuki; Osuka, Atsuhiro.

In: Journal of Physical Chemistry A, Vol. 105, No. 17, 03.05.2001, p. 4200-4210.

Research output: Contribution to journalArticle

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T1 - Excited-State Energy Transfer Processes in Phenylene- And Biphenylene-Linked and Directly-Linked Zinc(II) and Free-Base Hybrid Diporphyrins

AU - Sun Cho, Hyun

AU - Jeong, Dae Hong

AU - Yoon, Min Chul

AU - Kim, Yong Hee

AU - Kim, Yong Rok

AU - Kim, Dongho

AU - Jeoung, Sae Chae

AU - Kim, Seong Keun

AU - Aratani, Naoki

AU - Shinmori, Hideyuki

AU - Osuka, Atsuhiro

PY - 2001/5/3

Y1 - 2001/5/3

N2 - The photoinduced energy transfer processes in 1,4-phenylene-, 1,3-phenylene, 1,2-phenylene, and 4,4′-biphenylene-linked and directly-linked Zn(II)-free base porphyrin heterodimers in THF were investigated by femtosecond transient absorption spectroscopy. The energy transfer rates were compared between TPP-type and OEP-type heterodimers respectively as A2u-HOMO and A]U-HOMO subunits, for evaluating the relative contribution of the through-bond and through-space interactions. The rate difference becomes smaller with a decrease of spacer, more than 10 for 1,4-bis(phenylethynyl)phenylene and 1,4-diphenylethynylene, 4 for 4,4′-biphenylene-linked heterodimer, and 3 for 1,3- and 1,4-phenylene-linked spacers. In the meso-meso directlylinked case, the energy transfer rates are the same ((0.55 ps)-1) for 5,5,15,15-tetrakis(3,5-bis(octyloxy)phenyl)-substituted and 5,5,15,15-tetrakis(pentafluorophenyl)-substituted heterodimers, featuring only a minor influence of the frontier orbital characteristics on the energy transfer rate. The energy transfer rates are identical (0.55 ps)-1 for the directly-linked meso-meso heterodimers substituted with 3,5-bis(octyloxy)phenyl and pentafluorophenyl groups regardless of the difference in the HOMO orbital symmetry characteristics, suggesting the predominant Coulombic interaction for the energy transfer in these close proximity porphyrin dimers. In the case of 1,2-phenylene-linked heterodimers, the choice of the peripheral substituents can lead to a state-to-state rapid energy transfer with a rate of (0.55 ps-1) for the TPP-type model or a delocalized excimer-like diporphyrin excited state for the OEP-type model. Collectively, these results indicate that even for the covalently-linked models the relative contribution of the through-space Coulombic interaction becomes increasingly important upon the decrease of the center-to-center separation. Especially, the fast and efficient energy transfer occurring in the directly-linked heterodimer illustrates that this porphyrin unit can be utilized as a good candidate for energy transfer functional arrays in molecular photonic devices.

AB - The photoinduced energy transfer processes in 1,4-phenylene-, 1,3-phenylene, 1,2-phenylene, and 4,4′-biphenylene-linked and directly-linked Zn(II)-free base porphyrin heterodimers in THF were investigated by femtosecond transient absorption spectroscopy. The energy transfer rates were compared between TPP-type and OEP-type heterodimers respectively as A2u-HOMO and A]U-HOMO subunits, for evaluating the relative contribution of the through-bond and through-space interactions. The rate difference becomes smaller with a decrease of spacer, more than 10 for 1,4-bis(phenylethynyl)phenylene and 1,4-diphenylethynylene, 4 for 4,4′-biphenylene-linked heterodimer, and 3 for 1,3- and 1,4-phenylene-linked spacers. In the meso-meso directlylinked case, the energy transfer rates are the same ((0.55 ps)-1) for 5,5,15,15-tetrakis(3,5-bis(octyloxy)phenyl)-substituted and 5,5,15,15-tetrakis(pentafluorophenyl)-substituted heterodimers, featuring only a minor influence of the frontier orbital characteristics on the energy transfer rate. The energy transfer rates are identical (0.55 ps)-1 for the directly-linked meso-meso heterodimers substituted with 3,5-bis(octyloxy)phenyl and pentafluorophenyl groups regardless of the difference in the HOMO orbital symmetry characteristics, suggesting the predominant Coulombic interaction for the energy transfer in these close proximity porphyrin dimers. In the case of 1,2-phenylene-linked heterodimers, the choice of the peripheral substituents can lead to a state-to-state rapid energy transfer with a rate of (0.55 ps-1) for the TPP-type model or a delocalized excimer-like diporphyrin excited state for the OEP-type model. Collectively, these results indicate that even for the covalently-linked models the relative contribution of the through-space Coulombic interaction becomes increasingly important upon the decrease of the center-to-center separation. Especially, the fast and efficient energy transfer occurring in the directly-linked heterodimer illustrates that this porphyrin unit can be utilized as a good candidate for energy transfer functional arrays in molecular photonic devices.

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