論文

査読有り 国際誌
2017年11月

Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids

CHEMISTRY-A EUROPEAN JOURNAL
  • Keisuke Sudoh
  • ,
  • Takaharu Satoh
  • ,
  • Toru Amaya
  • ,
  • Ko Furukawa
  • ,
  • Mao Minoura
  • ,
  • Haruyuki Nakano
  • ,
  • Yoshihiro Matano

23
64
開始ページ
16364
終了ページ
16373
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1002/chem.201703664
出版者・発行元
WILEY-V C H VERLAG GMBH

In spite of significant advances in redox-active porphyrin-based materials and catalysts, little attention has been paid to 20 pi and 19 pi porphyrins because of their instability in air. Here we report the meso-modification of 5,10,15,20-tetraarylporphyrin with two nitrogen atoms, which led to redox-switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal-templated annulation of the corresponding metal-bis(dipyrrin) complexes. The inductive and resonance effects of the meso-nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP pi-systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and pi-pi* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the pi-systems. In contrast to the isoelectronic 5,10,15,20-tetraarylporphyrin derivatives, the 20 pi and 19 pi TADAPs were chemically stable under air. In particular, the 19 pi TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low-lying singly occupied molecular orbitals of their pi-systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19 pi/20 pi redox cycle.

リンク情報
DOI
https://doi.org/10.1002/chem.201703664
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/28895212
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000417968100030&DestApp=WOS_CPL
Scopus
https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85032260182&origin=inward
Scopus Citedby
https://www.scopus.com/inward/citedby.uri?partnerID=HzOxMe3b&scp=85032260182&origin=inward
ID情報
  • DOI : 10.1002/chem.201703664
  • ISSN : 0947-6539
  • eISSN : 1521-3765
  • ORCIDのPut Code : 51044788
  • PubMed ID : 28895212
  • SCOPUS ID : 85032260182
  • Web of Science ID : WOS:000417968100030

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