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. 2019 Sep 1;24(17):3177.
doi: 10.3390/molecules24173177.

A Convenient Synthesis of Pentaporphyrins and Supramolecular Complexes with a Fulleropyrrolidine

Joana I T Costa  1 , Andreia S F Farinha  2 , Filipe A Almeida Paz  3 , Augusto C Tomé  4
Affiliations

A Convenient Synthesis of Pentaporphyrins and Supramolecular Complexes with a Fulleropyrrolidine

Joana I T Costa et al. Molecules. .

Abstract

A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of the absorption and fluorescence spectra were observed upon addition of C60 to the porphyrin derivatives, the addition of PyC60 to the corresponding mono-Zn(II) porphyrins resulted in the formation of Zn(porphyrin)-PyC60 coordination complexes and the binding constants were calculated. Results show that the four free-base porphyrin units in pentaporphyrin 6 have a significant contribution in the stabilization of the 6-PyC60 complex. The crystal and molecular features of the pentaporphyrin Zn5 were unveiled using single-crystal X-ray diffraction studies.

Keywords: fullerene; multiporphyrin; supramolecular chemistry.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis of diporpyrins 3 and 4.
Figure 1
Figure 1
Molecular structures of pentaporphyrins 5, Zn5 and 6.
Figure 2
Figure 2
Absorption spectra of 1, Zn2, 4, and 6 in toluene. All compounds were used with a concentration of 1.0 μM. The inset shows an expansion of the Q bands.
Figure 3
Figure 3
Schematic representation of the pentaporphyrin molecular unit present in the crystal structure of Zn5·Solvent.
Figure 4
Figure 4
Absorption spectra of 6 (1.0 × 10−7 M) upon addition of PyC60 (0–113 equiv.) in toluene at 23 °C (upper part) and experimental data at 422 nm fitted to a non-linear 1:1 binding model (lower part).
Figure 5
Figure 5
Representation of the coordination complex 6–PyC60.
Figure 6
Figure 6
Fluorescence spectra (λexc = 428 nm) of 6 (1.0 × 10−7 M) upon addition of PyC60 (0–113 equiv.) in toluene at 23 °C (upper part) and experimental data at 650 nm fitted to a non-linear 1:1 binding model (lower part).
Figure 6
Figure 6
Fluorescence spectra (λexc = 428 nm) of 6 (1.0 × 10−7 M) upon addition of PyC60 (0–113 equiv.) in toluene at 23 °C (upper part) and experimental data at 650 nm fitted to a non-linear 1:1 binding model (lower part).
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References

    1. Aratani N., Takagi A., Yanagawa Y., Matsumoto T., Kawai T., Yoon Z.S., Kim D., Osuka A. Giant meso–meso-linked porphyrin arrays of micrometer molecular length and their fabrication. Chem. Eur. J. 2005;11:3389–3404. doi: 10.1002/chem.200401306. - DOI - PubMed
    1. Beletskaya I., Tyurin V.S., Tsivadze A.Y., Guilard R., Stern C. Supramolecular chemistry of metalloporphyrins. Chem. Rev. 2009;109:1659–1713. doi: 10.1021/cr800247a. - DOI - PubMed
    1. Drain C.M., Varotto A., Radivojevic I. Self-organized porphyrinic materials. Chem. Rev. 2009;109:1630–1658. doi: 10.1021/cr8002483. - DOI - PMC - PubMed
    1. Balaban T.S. Self-assembling porphyrins and chlorins as synthetic mimics of the chlorosomal bacteriochlorophylls. In: Kadish K.M., Smith K.M., Guilard R., editors. Handbook of Porphyrin Science. Volume 1. World Scientific; Singapore: 2010. pp. 221–306. Chapter 3.
    1. Morisue M., Kobuke Y. Supramolecular organization of porphyrins and phthalocyanines by use of biomimetic coordination methodology. In: Kadish K.M., Smith K.M., Guilard R., editors. Handbook of Porphyrin Science. Volume 32. World Scientific; Singapore: 2014. pp. 1–126. Chapter 166.

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