meso-aryl-substituted subporphyrins: Synthesis, structures, and large substituent effects on their electronic properties

Yasuhide Inokuma, Seok Yoon Zin, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

143 Citations (Scopus)

Abstract

Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine - tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0°C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. 1H NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90°C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130°C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7°) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7°). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.

Original languageEnglish
Pages (from-to)4747-4761
Number of pages15
JournalJournal of the American Chemical Society
Volume129
Issue number15
DOIs
Publication statusPublished - 2007 Apr 18

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Electronic properties
Chloroacetic acid
Fluorescence
Trifluoroacetic acid
Trifluoroacetic Acid
Porphyrins
Dihedral angle
Chromophores
Aldehydes
Excited states
Pyridine
Charge transfer
Cones
Condensation
Theoretical Models
Air
Nuclear magnetic resonance
X-Rays
X rays
Equipment and Supplies

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

@article{4804fd9472ed4d8bb72cf295f177c2bc,
title = "meso-aryl-substituted subporphyrins: Synthesis, structures, and large substituent effects on their electronic properties",
abstract = "Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine - tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2{\%}, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0°C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6{\%} yield. 1H NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90°C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130°C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7°) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7°). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.",
author = "Yasuhide Inokuma and Zin, {Seok Yoon} and Dongho Kim and Atsuhiro Osuka",
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meso-aryl-substituted subporphyrins : Synthesis, structures, and large substituent effects on their electronic properties. / Inokuma, Yasuhide; Zin, Seok Yoon; Kim, Dongho; Osuka, Atsuhiro.

In: Journal of the American Chemical Society, Vol. 129, No. 15, 18.04.2007, p. 4747-4761.

Research output: Contribution to journalArticle

TY - JOUR

T1 - meso-aryl-substituted subporphyrins

T2 - Synthesis, structures, and large substituent effects on their electronic properties

AU - Inokuma, Yasuhide

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N2 - Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine - tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0°C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. 1H NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90°C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130°C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7°) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7°). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.

AB - Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine - tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0°C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. 1H NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90°C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130°C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7°) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7°). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.

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