Synthesis, Characterization, MCD Spectroscopy, and TD-DFT Calculations of Copper-Metalated Nonperipherally Substituted Octaoctyl Derivatives of Tetrabenzotriazaporphyrin, <i>cis</i>- and <i>trans</i>-Tetrabenzodiazaporphyrin, Tetrabenzomonoazaporphyrin, and Tetrabenzoporphyrin
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- John Mack
- Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
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- Lydia Sosa-Vargas
- School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.
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- Simon J. Coles
- EPSRC National Crystallography Service, School of Chemistry, University of Southampton, Southampton SO17 1BJ, U.K.
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- Graham J. Tizzard
- EPSRC National Crystallography Service, School of Chemistry, University of Southampton, Southampton SO17 1BJ, U.K.
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- Isabelle Chambrier
- School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.
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- Andrew N. Cammidge
- School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.
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- Michael J. Cook
- School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.
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- Nagao Kobayashi
- Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
書誌事項
- 公開日
- 2012-11-09
- 資源種別
- journal article
- DOI
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- 10.1021/ic301712h
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
Synthesis of the title compounds has been achieved through refinement of a recently reported synthetic protocol whereby varying equivalents of MeMgBr are reacted with 1,4-dioctylphthalonitrile to produce mixtures favoring specific hybrid structures. The initially formed magnesium-metalated compounds are obtained as pure materials and include, for the first time, both isomers (cis and trans) of tetrabenzodiazaporphyrin. The compounds were demetalated to the metal-free analogues, which were then converted into the copper-metalated derivatives. The X-ray structure of the copper tetrabenzotriazaporphyrin derivative is reported. The metal-free and copper-metalated macrocycles exhibit columnar mesophase behavior, and it is found that the mesophase stability is unexpectedly reduced in the diazaporphyrin derivatives compared to the rest of the series. The results of time-dependent density functional theory calculations for the copper complexes are compared to the observed optical properties. Michl's perimeter model was used as a conceptual framework for analyzing the magnetic circular dichroism spectral data, which predicted and accounted for trends in the observed experimental spectra.
収録刊行物
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- Inorganic Chemistry
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Inorganic Chemistry 51 (23), 12820-12833, 2012-11-09
American Chemical Society (ACS)
