Photochemistry of covalently-linked multi-porphyrinic systems

Naoki Aratani, Atsuhiro Osuka, Hyun Sun Cho, Dongho Kim

Research output: Contribution to journalReview article

132 Citations (Scopus)

Abstract

Synthesis, structural characteristics, and optical and electrochemical properties of various covalently-linked porphyrin arrays are described. First, aromatic-spacer bridged diporphyrins were prepared in which the diporphyrin geometries were conformationally-restricted and thus suitable for detailed studies on the exciton coupling and the intramolecular energy and/or electron transfer reactions. Secondly, the Ag(I)-salt oxidation of 5,15-diaryl Zn(II) porphyrins provided meso-meso-linked Zn(II)-diporphyrins. This reaction is advantageous in light of its high regioselectivity and easy extension to longer porphyrin arrays. The doubling reaction was repeated up to the synthesis of a discrete 128-mer, which is, to the best of our knowledge, the longest man-made molecule. Finally, the oxidation of meso-meso-linked Zn(II) porphyrin arrays with a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and Sc(III)(OTf)3 produced fused porphyrin arrays with full π-conjugation, which displayed extremely small HOMO-LUMO gaps that reach into the infrared region.

Original languageEnglish
Pages (from-to)25-52
Number of pages28
JournalJournal of Photochemistry and Photobiology C: Photochemistry Reviews
Volume3
Issue number1
DOIs
Publication statusPublished - 2002 Jan 1

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Photochemical reactions
Porphyrins
porphyrins
photochemical reactions
Regioselectivity
Oxidation
oxidation
quinones
synthesis
conjugation
Electrochemical properties
Excitons
spacers
electron transfer
Optical properties
Salts
excitons
salts
Infrared radiation
optical properties

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

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title = "Photochemistry of covalently-linked multi-porphyrinic systems",
abstract = "Synthesis, structural characteristics, and optical and electrochemical properties of various covalently-linked porphyrin arrays are described. First, aromatic-spacer bridged diporphyrins were prepared in which the diporphyrin geometries were conformationally-restricted and thus suitable for detailed studies on the exciton coupling and the intramolecular energy and/or electron transfer reactions. Secondly, the Ag(I)-salt oxidation of 5,15-diaryl Zn(II) porphyrins provided meso-meso-linked Zn(II)-diporphyrins. This reaction is advantageous in light of its high regioselectivity and easy extension to longer porphyrin arrays. The doubling reaction was repeated up to the synthesis of a discrete 128-mer, which is, to the best of our knowledge, the longest man-made molecule. Finally, the oxidation of meso-meso-linked Zn(II) porphyrin arrays with a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and Sc(III)(OTf)3 produced fused porphyrin arrays with full π-conjugation, which displayed extremely small HOMO-LUMO gaps that reach into the infrared region.",
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Photochemistry of covalently-linked multi-porphyrinic systems. / Aratani, Naoki; Osuka, Atsuhiro; Cho, Hyun Sun; Kim, Dongho.

In: Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 3, No. 1, 01.01.2002, p. 25-52.

Research output: Contribution to journalReview article

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AB - Synthesis, structural characteristics, and optical and electrochemical properties of various covalently-linked porphyrin arrays are described. First, aromatic-spacer bridged diporphyrins were prepared in which the diporphyrin geometries were conformationally-restricted and thus suitable for detailed studies on the exciton coupling and the intramolecular energy and/or electron transfer reactions. Secondly, the Ag(I)-salt oxidation of 5,15-diaryl Zn(II) porphyrins provided meso-meso-linked Zn(II)-diporphyrins. This reaction is advantageous in light of its high regioselectivity and easy extension to longer porphyrin arrays. The doubling reaction was repeated up to the synthesis of a discrete 128-mer, which is, to the best of our knowledge, the longest man-made molecule. Finally, the oxidation of meso-meso-linked Zn(II) porphyrin arrays with a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and Sc(III)(OTf)3 produced fused porphyrin arrays with full π-conjugation, which displayed extremely small HOMO-LUMO gaps that reach into the infrared region.

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