Photochemistry of covalently-linked multi-porphyrinic systems

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

Research output: Contribution to journalReview articlepeer-review

136 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

Bibliographical note

Funding Information:
The authors thank collaborators at Kyoto University and Yonsei University for their contributions to this work. We are grateful to Prof. I. Yamazaki, Drs. T. Yamazaki, and Y. Nishimura for fluorescence measurements, and Prof. N. Ohta at Hokkaido University for the electro-absorption measurements. NA thanks the JSPS Research Fellowship for Young Scientists.

Funding Information:
Dongho Kim was born on 1 November 1957 in Seoul, Korea. He received BS degree in 1980 from Seoul National University and PhD degree in August 1984 at Washington University under the supervision of Prof. Dewey Holten. After that he moved to Princeton University as a postdoctoral fellow, where he worked at Prof. Thomas Spiro’s laboratory until the end of 1985. In 1986, he joined the Korea Research Institute of Standards and Science as a senior research scientist, where he has investigated time-resolved laser spectroscopy of various materials until August of 2000. He moved to Department of Chemistry, Yonsei University as a full professor in September 2000. During 1998, he was a visiting scientist at Prof. Keitaro Yoshihara’s laboratory of the Institute for Molecular Science, Japan. He also was a visiting professor at Washington University in 1997. Since 1997, he has been leading the Center for Ultrafast Optical Characteristics Control supported by the National Creative Research Initiatives Program of the Ministry of Science and Technology of Korea.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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