TY - JOUR
T1 - Redox-switchable 20π-, 19π-, and 18π-electron 5,10,15,20-tetraaryl-5,15-diazaporphyrinoid nickel(II) complexes
AU - Satoh, Takaharu
AU - Minoura, Mao
AU - Nakano, Haruyuki
AU - Furukawa, Ko
AU - Matano, Yoshihiro
N1 - Funding Information:
This work was supported by JSPS KAKENHI (15H00931 to Y.M., 15H00962 to M.M., and 24109008 and 25287091 to K.F.).
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/2/5
Y1 - 2016/2/5
N2 - The first examples of air-stable 20π-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18π-electron dications, and the 19π-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20π-electron derivatives are antiaromatic and the cationic 18π-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins. N makes all the difference: Redox-switchable 20π-, 19π-, and 18π-electron 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids are prepared through metal-templated annulation of NiII bis(dipyrrin) complexes followed by oxidation. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins.
AB - The first examples of air-stable 20π-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18π-electron dications, and the 19π-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20π-electron derivatives are antiaromatic and the cationic 18π-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins. N makes all the difference: Redox-switchable 20π-, 19π-, and 18π-electron 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids are prepared through metal-templated annulation of NiII bis(dipyrrin) complexes followed by oxidation. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins.
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U2 - 10.1002/anie.201510734
DO - 10.1002/anie.201510734
M3 - Article
AN - SCOPUS:84957841797
SN - 1433-7851
VL - 55
SP - 2235
EP - 2238
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 6
ER -