Synthesis and Properties of Fused-Ring-Expanded Porphyrins that were Core-Modified with Group 16 Heteroatoms

Authors

  • Dr. Hai-Jun Xu,

    1. State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25–8331–4502
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    • These authors contributed equally to this work.

  • Dr. John Mack,

    1. Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980–8578 (Japan), Fax: (+81) 22–795–7719
    2. Current address: Department of Chemistry, Rhodes University, Grahamstown (South Africa)
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  • Dr. Di Wu,

    1. State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25–8331–4502
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    • These authors contributed equally to this work.

  • Dr. Zhao-Li Xue,

    1. State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25–8331–4502
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    • These authors contributed equally to this work.

  • Dr. Ana B. Descalzo,

    1. Division 1.9 Sensor Materials, BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Strasse 11, 12489 Berlin (Germany), Fax: (+49) 30–8104–1157
    2. Current address: Department of Organic Chemistry, Faculty of Chemical Sciences, Complutense University of Madrid, Avda. Complutense s/n, 28040 Madrid (Spain)
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  • Dr. Knut Rurack,

    Corresponding author
    1. Division 1.9 Sensor Materials, BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Strasse 11, 12489 Berlin (Germany), Fax: (+49) 30–8104–1157
    • Division 1.9 Sensor Materials, BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Strasse 11, 12489 Berlin (Germany), Fax: (+49) 30–8104–1157
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  • Prof. Nagao Kobayashi,

    Corresponding author
    1. Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980–8578 (Japan), Fax: (+81) 22–795–7719
    • Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980–8578 (Japan), Fax: (+81) 22–795–7719
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  • Prof. Zhen Shen

    Corresponding author
    1. State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25–8331–4502
    • State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25–8331–4502
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Abstract

The synthesis of a series of novel core-modified and fused-ring-expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem-crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine-tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso-phenyl rings, is also examined.

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