Homoconjugation in diporphyrins

Excitonic behaviors in singly and doubly linked Zn(ii)porphyrin dimers

Min Chul Yoon, Sangsu Lee, Sumito Tokuji, Hideki Yorimitsu, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

We have comparatively investigated excitonic features between singly and doubly alkyl bridged Zn(ii)porphyrin dimers (SLZn and DLZn, respectively) with Zn(ii)tetraphenylporphyrin (ZnTPP) as a reference by using various time-resolved anisotropy measurements. Time-resolved fluorescence anisotropy decay of the B-state of ZnTPP in toluene showed ultrafast dephasing times of 83 and 185 fs with an initial anisotropy value (r0) of ∼0.7 being consistent with the theoretically proposed one. On the other hand, the Q-state of ZnTPP exhibited a depolarization time of 120 fs with a smaller r0of 0.25 than that of the B-state because of probing photo-induced absorption in transient absorption anisotropy measurements. Spectroscopic features in absorption, fluorescence, and excitation anisotropy spectra of SLZn are similar to those of ZnTPP indicating a relatively weak exciton coupling in the Q-state. As a result, the observed depolarization time with a time-constant of 1.4 ps can be explained by a Förster-type incoherent energy transfer process between two constituent subunits. When compared to ZnTPP and SLZn however, DLZn exhibited very different optical characteristics such as more red-shifted absorption and emission spectra, three times larger fluorescence excitation anisotropy values, and ultrafast sign inversion in transient absorption anisotropy. According to these results, it can be inferred that the overall π-electron densities of the electronic excited states in DLZn are fully delocalized in a whole dimer and that DLZn can be regarded as a coherently coupled single quantum system not as separate individual chromophores. Frontier π-molecular orbital structures as well as electron density difference maps between occupied and unoccupied molecular orbitals involved in the electron promotions for underlying excited states clearly represent weakly and strongly exciton-coupled natures of SLZn and DLZn, respectively. Accordingly, the extended conjugation of π-electrons over the whole DLZn molecule demonstrates an example for homoconjugation between two aromatic porphyrins.

Original languageEnglish
Pages (from-to)1756-1764
Number of pages9
JournalChemical Science
Volume4
Issue number4
DOIs
Publication statusPublished - 2013 Mar 4

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Porphyrins
Dimers
Anisotropy
Fluorescence
Depolarization
Molecular orbitals
Excited states
Carrier concentration
Electrons
Toluene
Chromophores
Energy transfer
tetraphenylporphyrin
Molecules

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Yoon, Min Chul ; Lee, Sangsu ; Tokuji, Sumito ; Yorimitsu, Hideki ; Osuka, Atsuhiro ; Kim, Dongho. / Homoconjugation in diporphyrins : Excitonic behaviors in singly and doubly linked Zn(ii)porphyrin dimers. In: Chemical Science. 2013 ; Vol. 4, No. 4. pp. 1756-1764.
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abstract = "We have comparatively investigated excitonic features between singly and doubly alkyl bridged Zn(ii)porphyrin dimers (SLZn and DLZn, respectively) with Zn(ii)tetraphenylporphyrin (ZnTPP) as a reference by using various time-resolved anisotropy measurements. Time-resolved fluorescence anisotropy decay of the B-state of ZnTPP in toluene showed ultrafast dephasing times of 83 and 185 fs with an initial anisotropy value (r0) of ∼0.7 being consistent with the theoretically proposed one. On the other hand, the Q-state of ZnTPP exhibited a depolarization time of 120 fs with a smaller r0of 0.25 than that of the B-state because of probing photo-induced absorption in transient absorption anisotropy measurements. Spectroscopic features in absorption, fluorescence, and excitation anisotropy spectra of SLZn are similar to those of ZnTPP indicating a relatively weak exciton coupling in the Q-state. As a result, the observed depolarization time with a time-constant of 1.4 ps can be explained by a F{\"o}rster-type incoherent energy transfer process between two constituent subunits. When compared to ZnTPP and SLZn however, DLZn exhibited very different optical characteristics such as more red-shifted absorption and emission spectra, three times larger fluorescence excitation anisotropy values, and ultrafast sign inversion in transient absorption anisotropy. According to these results, it can be inferred that the overall π-electron densities of the electronic excited states in DLZn are fully delocalized in a whole dimer and that DLZn can be regarded as a coherently coupled single quantum system not as separate individual chromophores. Frontier π-molecular orbital structures as well as electron density difference maps between occupied and unoccupied molecular orbitals involved in the electron promotions for underlying excited states clearly represent weakly and strongly exciton-coupled natures of SLZn and DLZn, respectively. Accordingly, the extended conjugation of π-electrons over the whole DLZn molecule demonstrates an example for homoconjugation between two aromatic porphyrins.",
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Homoconjugation in diporphyrins : Excitonic behaviors in singly and doubly linked Zn(ii)porphyrin dimers. / Yoon, Min Chul; Lee, Sangsu; Tokuji, Sumito; Yorimitsu, Hideki; Osuka, Atsuhiro; Kim, Dongho.

In: Chemical Science, Vol. 4, No. 4, 04.03.2013, p. 1756-1764.

Research output: Contribution to journalArticle

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AU - Yoon, Min Chul

AU - Lee, Sangsu

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AU - Kim, Dongho

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AB - We have comparatively investigated excitonic features between singly and doubly alkyl bridged Zn(ii)porphyrin dimers (SLZn and DLZn, respectively) with Zn(ii)tetraphenylporphyrin (ZnTPP) as a reference by using various time-resolved anisotropy measurements. Time-resolved fluorescence anisotropy decay of the B-state of ZnTPP in toluene showed ultrafast dephasing times of 83 and 185 fs with an initial anisotropy value (r0) of ∼0.7 being consistent with the theoretically proposed one. On the other hand, the Q-state of ZnTPP exhibited a depolarization time of 120 fs with a smaller r0of 0.25 than that of the B-state because of probing photo-induced absorption in transient absorption anisotropy measurements. Spectroscopic features in absorption, fluorescence, and excitation anisotropy spectra of SLZn are similar to those of ZnTPP indicating a relatively weak exciton coupling in the Q-state. As a result, the observed depolarization time with a time-constant of 1.4 ps can be explained by a Förster-type incoherent energy transfer process between two constituent subunits. When compared to ZnTPP and SLZn however, DLZn exhibited very different optical characteristics such as more red-shifted absorption and emission spectra, three times larger fluorescence excitation anisotropy values, and ultrafast sign inversion in transient absorption anisotropy. According to these results, it can be inferred that the overall π-electron densities of the electronic excited states in DLZn are fully delocalized in a whole dimer and that DLZn can be regarded as a coherently coupled single quantum system not as separate individual chromophores. Frontier π-molecular orbital structures as well as electron density difference maps between occupied and unoccupied molecular orbitals involved in the electron promotions for underlying excited states clearly represent weakly and strongly exciton-coupled natures of SLZn and DLZn, respectively. Accordingly, the extended conjugation of π-electrons over the whole DLZn molecule demonstrates an example for homoconjugation between two aromatic porphyrins.

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