Versatile photophysical properties of meso-aryl-substituted subporphyrins

Dipolar and octupolar charge-transfer interactions

Shanmugam Easwaramoorthi, Jae Yoon Shin, Sung Cho, Pyosang Kim, Yasuhide Inokuma, Eiji Tsurumaki, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM=10 -50 cm 4 sphoton -1 ) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found betweenthe electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, paminophenyl≥ m-aminophenyl≥nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino-and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.

Original languageEnglish
Pages (from-to)12005-12017
Number of pages13
JournalChemistry - A European Journal
Volume15
Issue number44
DOIs
Publication statusPublished - 2009 Dec 1

Fingerprint

Charge transfer
Photons
Isomers
Substitution reactions
Fluorescence
Photoexcitation
Crystal symmetry
Toluene
Acetonitrile
Excited states
Stabilization
Molecules
Electrons
Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Easwaramoorthi, Shanmugam ; Shin, Jae Yoon ; Cho, Sung ; Kim, Pyosang ; Inokuma, Yasuhide ; Tsurumaki, Eiji ; Osuka, Atsuhiro ; Kim, Dongho. / Versatile photophysical properties of meso-aryl-substituted subporphyrins : Dipolar and octupolar charge-transfer interactions. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 44. pp. 12005-12017.
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abstract = "Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM=10 -50 cm 4 sphoton -1 ) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found betweenthe electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, paminophenyl≥ m-aminophenyl≥nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino-and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.",
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Versatile photophysical properties of meso-aryl-substituted subporphyrins : Dipolar and octupolar charge-transfer interactions. / Easwaramoorthi, Shanmugam; Shin, Jae Yoon; Cho, Sung; Kim, Pyosang; Inokuma, Yasuhide; Tsurumaki, Eiji; Osuka, Atsuhiro; Kim, Dongho.

In: Chemistry - A European Journal, Vol. 15, No. 44, 01.12.2009, p. 12005-12017.

Research output: Contribution to journalArticle

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T1 - Versatile photophysical properties of meso-aryl-substituted subporphyrins

T2 - Dipolar and octupolar charge-transfer interactions

AU - Easwaramoorthi, Shanmugam

AU - Shin, Jae Yoon

AU - Cho, Sung

AU - Kim, Pyosang

AU - Inokuma, Yasuhide

AU - Tsurumaki, Eiji

AU - Osuka, Atsuhiro

AU - Kim, Dongho

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N2 - Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM=10 -50 cm 4 sphoton -1 ) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found betweenthe electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, paminophenyl≥ m-aminophenyl≥nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino-and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.

AB - Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM=10 -50 cm 4 sphoton -1 ) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found betweenthe electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, paminophenyl≥ m-aminophenyl≥nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino-and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.

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