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Synthesis,Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems |
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| Authors: | Prof. Dr. Tetsuo Okujima Dr. John Mack Dr. Jun Nakamura Gugu Kubheka Prof. Dr. Tebello Nyokong Dr. Hua Zhu Naoki Komobuchi Prof. Dr. Noboru Ono Prof. Dr. Hiroko Yamada Prof. Dr. Hidemitsu Uno Prof. Dr. Nagao Kobayashi |
| Affiliation: | 1. Graduate School of Science and Engineering, Ehime University, Matsuyama, Japan;2. Department of Chemistry, Rhodes University, Grahamstown, South Africa;3. Graduate School of Science, Tohoku University, Sendai, Japan;4. Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma, Japan;5. Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan |
| Abstract: | A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π‐molecular orbitals. |
| Keywords: | cycloaddition density functional calculations fused-ring systems magnetic circular dichroism porphyrinoids |