Nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins and pyridazine-fused diazacorrinoids: Metal-template syntheses and peripheral functionalizations

Yoshihiro Matano, Tarou Shibano, Haruyuki Nakano, Hiroshi Imahori

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu) and pyridazine-fused diazacorrinoids (Ni-DACX; X=N, O). These two classes of compounds were constructed starting from mesityldipyrromethane by a metal-template method. Ni-DAP and Cu-DAP were prepared in high yields by the reaction of the respective metal-bis(dibromodipyrrin) complexes with NaN 3-CuX (X=I, Br), whereas Ni-DACN and Ni-DACO were formed as predominant products by the reaction with NaN 3. In both cases, the metal centers change their geometry from tetrahedral to square planar during the aza-annulation; X-ray crystallographic analyses of M-DAPs showed highly planar diazaporphyrin π planes. The Q band of Ni-DAP was redshifted and intensified compared with that of a nickel-porphyrin reference, due to the involvement of electronegative nitrogen atoms at the meso positions. It was found that the peripheral bromination of Ni-DAP and Ni-DACO occurred regioselectively to afford Ni-DAP-Br 4 and Ni-DACO-Br, respectively. These brominated derivatives underwent Stille reactions with tributyl(phenyl)stannane to give the corresponding phenylated derivatives, Ni-DAP-Ph 4 and Ni-DACO-Ph. On the basis of the absorption spectra and X-ray analysis, it has been concluded that the attached phenyl groups efficiently conjugate with the diazaporphyrin π system. The present results unambiguously corroborate that the β-unsubstituted DAPs and DACXs are promising platforms for the development of a new class of π-conjugated azaporphyrin-based materials.

Original languageEnglish
Pages (from-to)6208-6216
Number of pages9
JournalChemistry - A European Journal
Volume18
Issue number20
DOIs
Publication statusPublished - May 14 2012

Fingerprint

Nickel
Copper
Metals
Derivatives
Porphyrins
X ray analysis
Electrochemical properties
Absorption spectra
Nitrogen
Optical properties
X rays
Atoms
Geometry
pyridazine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins and pyridazine-fused diazacorrinoids : Metal-template syntheses and peripheral functionalizations. / Matano, Yoshihiro; Shibano, Tarou; Nakano, Haruyuki; Imahori, Hiroshi.

In: Chemistry - A European Journal, Vol. 18, No. 20, 14.05.2012, p. 6208-6216.

Research output: Contribution to journalArticle

@article{861c0b66f39c4e1db1fcbe16ec106f61,
title = "Nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins and pyridazine-fused diazacorrinoids: Metal-template syntheses and peripheral functionalizations",
abstract = "The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu) and pyridazine-fused diazacorrinoids (Ni-DACX; X=N, O). These two classes of compounds were constructed starting from mesityldipyrromethane by a metal-template method. Ni-DAP and Cu-DAP were prepared in high yields by the reaction of the respective metal-bis(dibromodipyrrin) complexes with NaN 3-CuX (X=I, Br), whereas Ni-DACN and Ni-DACO were formed as predominant products by the reaction with NaN 3. In both cases, the metal centers change their geometry from tetrahedral to square planar during the aza-annulation; X-ray crystallographic analyses of M-DAPs showed highly planar diazaporphyrin π planes. The Q band of Ni-DAP was redshifted and intensified compared with that of a nickel-porphyrin reference, due to the involvement of electronegative nitrogen atoms at the meso positions. It was found that the peripheral bromination of Ni-DAP and Ni-DACO occurred regioselectively to afford Ni-DAP-Br 4 and Ni-DACO-Br, respectively. These brominated derivatives underwent Stille reactions with tributyl(phenyl)stannane to give the corresponding phenylated derivatives, Ni-DAP-Ph 4 and Ni-DACO-Ph. On the basis of the absorption spectra and X-ray analysis, it has been concluded that the attached phenyl groups efficiently conjugate with the diazaporphyrin π system. The present results unambiguously corroborate that the β-unsubstituted DAPs and DACXs are promising platforms for the development of a new class of π-conjugated azaporphyrin-based materials.",
author = "Yoshihiro Matano and Tarou Shibano and Haruyuki Nakano and Hiroshi Imahori",
year = "2012",
month = "5",
day = "14",
doi = "10.1002/chem.201200463",
language = "English",
volume = "18",
pages = "6208--6216",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "20",

}

TY - JOUR

T1 - Nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins and pyridazine-fused diazacorrinoids

T2 - Metal-template syntheses and peripheral functionalizations

AU - Matano, Yoshihiro

AU - Shibano, Tarou

AU - Nakano, Haruyuki

AU - Imahori, Hiroshi

PY - 2012/5/14

Y1 - 2012/5/14

N2 - The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu) and pyridazine-fused diazacorrinoids (Ni-DACX; X=N, O). These two classes of compounds were constructed starting from mesityldipyrromethane by a metal-template method. Ni-DAP and Cu-DAP were prepared in high yields by the reaction of the respective metal-bis(dibromodipyrrin) complexes with NaN 3-CuX (X=I, Br), whereas Ni-DACN and Ni-DACO were formed as predominant products by the reaction with NaN 3. In both cases, the metal centers change their geometry from tetrahedral to square planar during the aza-annulation; X-ray crystallographic analyses of M-DAPs showed highly planar diazaporphyrin π planes. The Q band of Ni-DAP was redshifted and intensified compared with that of a nickel-porphyrin reference, due to the involvement of electronegative nitrogen atoms at the meso positions. It was found that the peripheral bromination of Ni-DAP and Ni-DACO occurred regioselectively to afford Ni-DAP-Br 4 and Ni-DACO-Br, respectively. These brominated derivatives underwent Stille reactions with tributyl(phenyl)stannane to give the corresponding phenylated derivatives, Ni-DAP-Ph 4 and Ni-DACO-Ph. On the basis of the absorption spectra and X-ray analysis, it has been concluded that the attached phenyl groups efficiently conjugate with the diazaporphyrin π system. The present results unambiguously corroborate that the β-unsubstituted DAPs and DACXs are promising platforms for the development of a new class of π-conjugated azaporphyrin-based materials.

AB - The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu) and pyridazine-fused diazacorrinoids (Ni-DACX; X=N, O). These two classes of compounds were constructed starting from mesityldipyrromethane by a metal-template method. Ni-DAP and Cu-DAP were prepared in high yields by the reaction of the respective metal-bis(dibromodipyrrin) complexes with NaN 3-CuX (X=I, Br), whereas Ni-DACN and Ni-DACO were formed as predominant products by the reaction with NaN 3. In both cases, the metal centers change their geometry from tetrahedral to square planar during the aza-annulation; X-ray crystallographic analyses of M-DAPs showed highly planar diazaporphyrin π planes. The Q band of Ni-DAP was redshifted and intensified compared with that of a nickel-porphyrin reference, due to the involvement of electronegative nitrogen atoms at the meso positions. It was found that the peripheral bromination of Ni-DAP and Ni-DACO occurred regioselectively to afford Ni-DAP-Br 4 and Ni-DACO-Br, respectively. These brominated derivatives underwent Stille reactions with tributyl(phenyl)stannane to give the corresponding phenylated derivatives, Ni-DAP-Ph 4 and Ni-DACO-Ph. On the basis of the absorption spectra and X-ray analysis, it has been concluded that the attached phenyl groups efficiently conjugate with the diazaporphyrin π system. The present results unambiguously corroborate that the β-unsubstituted DAPs and DACXs are promising platforms for the development of a new class of π-conjugated azaporphyrin-based materials.

UR - http://www.scopus.com/inward/record.url?scp=84860774459&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84860774459&partnerID=8YFLogxK

U2 - 10.1002/chem.201200463

DO - 10.1002/chem.201200463

M3 - Article

C2 - 22473518

AN - SCOPUS:84860774459

VL - 18

SP - 6208

EP - 6216

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 20

ER -