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
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- 巻
- 23
- 号
- 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
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- 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
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- 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