Covalently linked 5,15-diazaporphyrin dimers: Promising scaffolds for a highly conjugated azaporphyrin π system

Yoshihiro Matano, Daisuke Fujii, Tarou Shibano, Ko Furukawa, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The first examples of β-β directly linked, acetylene-bridged, and butadiyne-bridged 5,15-diazaporphyrin dimers have been prepared by palladium-catalyzed coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl=2,4,6-trimethylphenyl). The effects of the linking modes and meso-nitrogen atoms on the structural, optical, electrochemical, and magnetic properties of the distributed π systems were investigated by using X-ray crystallography, UV/Vis absorption spectroscopy, DFT calculations, cyclic voltammetry, and ESR spectroscopy. Both the electronic and steric effects of the meso-nitrogen atoms play an important role in the highly coplanar geometry of the directly linked dimers. The direct β-β linkage produces enhanced π conjugation and electron-spin coupling between the two diazaporphyrin units.

Original languageEnglish
Pages (from-to)3342-3349
Number of pages8
JournalChemistry - A European Journal
Volume20
Issue number12
DOIs
Publication statusPublished - Mar 17 2014

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Scaffolds
Dimers
Nitrogen
Acetylene
Atoms
X ray crystallography
Palladium
Nickel
Ultraviolet spectroscopy
Electrochemical properties
Absorption spectroscopy
Discrete Fourier transforms
Cyclic voltammetry
Paramagnetic resonance
Structural properties
Copper
Magnetic properties
Optical properties
Spectroscopy
Geometry

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Covalently linked 5,15-diazaporphyrin dimers : Promising scaffolds for a highly conjugated azaporphyrin π system. / Matano, Yoshihiro; Fujii, Daisuke; Shibano, Tarou; Furukawa, Ko; Higashino, Tomohiro; Nakano, Haruyuki; Imahori, Hiroshi.

In: Chemistry - A European Journal, Vol. 20, No. 12, 17.03.2014, p. 3342-3349.

Research output: Contribution to journalArticle

Matano, Yoshihiro ; Fujii, Daisuke ; Shibano, Tarou ; Furukawa, Ko ; Higashino, Tomohiro ; Nakano, Haruyuki ; Imahori, Hiroshi. / Covalently linked 5,15-diazaporphyrin dimers : Promising scaffolds for a highly conjugated azaporphyrin π system. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 12. pp. 3342-3349.
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