Redox switchable 19 π and 18 π 5,10,20-triaryl-5,15-diazaporphyrinoid-nickel(II) complexes

Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)-bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the N-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18π (cation) and 19π (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP π-system. NMR spectroscopy of the 18π TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19π TriADAP showed a highly delocalized electron spin of the π-radical. The para substituents of the N-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic β-protons observed in the 1H NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18π-19π redox-switchable optical and magnetic properties.

Original languageEnglish
Pages (from-to)542-551
Number of pages10
JournalJournal of Porphyrins and Phthalocyanines
Volume22
Issue number7
DOIs
Publication statusPublished - Jul 1 2018

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Nickel
Optical properties
Cations
Magnetic properties
Electrons
Cyclization
Electrochemical properties
Shielding
Nuclear magnetic resonance spectroscopy
Hydrogenation
Paramagnetic resonance
Protons
Metals
Nuclear magnetic resonance
Spectroscopy
Oxidation
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Redox switchable 19 π and 18 π 5,10,20-triaryl-5,15-diazaporphyrinoid-nickel(II) complexes. / Sudoh, Keisuke; Hatakeyama, Takuroh; Furukawa, Ko; Nakano, Haruyuki; Matano, Yoshihiro.

In: Journal of Porphyrins and Phthalocyanines, Vol. 22, No. 7, 01.07.2018, p. 542-551.

Research output: Contribution to journalArticle

Sudoh, Keisuke ; Hatakeyama, Takuroh ; Furukawa, Ko ; Nakano, Haruyuki ; Matano, Yoshihiro. / Redox switchable 19 π and 18 π 5,10,20-triaryl-5,15-diazaporphyrinoid-nickel(II) complexes. In: Journal of Porphyrins and Phthalocyanines. 2018 ; Vol. 22, No. 7. pp. 542-551.
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abstract = "The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)-bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the N-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18π (cation) and 19π (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP π-system. NMR spectroscopy of the 18π TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19π TriADAP showed a highly delocalized electron spin of the π-radical. The para substituents of the N-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic β-protons observed in the 1H NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18π-19π redox-switchable optical and magnetic properties.",
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AB - The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)-bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the N-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18π (cation) and 19π (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP π-system. NMR spectroscopy of the 18π TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19π TriADAP showed a highly delocalized electron spin of the π-radical. The para substituents of the N-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic β-protons observed in the 1H NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18π-19π redox-switchable optical and magnetic properties.

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