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MCD spectroscopy and TD-DFT calculations of low-symmetry acenaphthoporphyrins with dual fluorescence

Department of Chemistry, Rhodes University, Grahamstown 6140, South Africa

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan

SPP full member in good standing.

Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan

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Tetsuo Okujima

Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan

Corresponding author, fax: +81 89-927-9615.

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Hiroko Yamada

Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma 630-0192, Japan

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Hidemitsu Uno

Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan

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, and

Nagao Kobayashi

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan

Corresponding author, fax: +81 22-795-7719.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424613500727Cited by:3 (Source: Crossref)

Abstract

Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations are used to analyze the electronic structure and optical properties of low-symmetry acenaphthoporphyrins with AAAB, ABAB and AABB structures. Evidence for dual fluorescence caused by tautomerism has been identified in the emission spectra of the AAAB and ABAB compounds. The sign sequences observed for the Q and B bands in the MCD spectra have been used to validate the results of the TD-DFT calculations. An anomalous +/- sign sequence is observed in the B band region with ascending energy similar to that reported previously for metal tetraphenyltetraacenaphthoporphyrin complexes.

Dedicated to Professor Vefa Ahsen on the occasion of his 60th birthday

Keywords:

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