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Syntheses and CO2 reduction activities of π-expanded/extended iron porphyrin complexes

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Abstract

The construction of molecular catalysts that are active toward CO2 reduction is of great significance for designing sustainable energy conversion systems. In this study, we aimed to develop catalysts for CO2 reduction by introducing aromatic substituents to the meso-positions of iron porphyrin complexes. Three novel iron porphyrin complexes with π-expanded substituents (5,10,15,20-tetrakis(pyren-1-yl)porphyrinato iron(III) chloride (Fe-Py)), π-extended substituents (5,10,15,20-tetrakis((1,1′-biphenyl)-4-yl)porphyrinato iron(III) chloride (Fe-PPh)) and π-expanded and extended substituents (5,10,15,20-tetrakis(4-(pyren-1-yl)phenyl)porphyrinato iron(III) chloride (Fe-PPy)) were successfully synthesized, and their physical properties were investigated by UV–vis absorption spectroscopy and electrochemical measurements under Ar in comparison with an iron complex with a basic framework, 5,10,15,20-tetrakis(phenyl)porphyrinato iron(III) chloride (Fe-Ph). Moreover, the catalytic activity of the complexes was studied by electrochemical measurements under CO2, and it is found that the complex with the π-expanded substituents exhibits the highest activity among these complexes.

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Notes

  1. In the iron porphyrin complexes, there are several possible resonant forms to describe the electronic structure of the reduced species, and all resonant forms presumably contribute to the electronic structure of the complexes. In the case of Fe-Ph, previous reports suggested that the three electron reduced species should be best formulated as a Fe(0) complex, based on the results of UV–vis and resonance Raman spectroscopy and the studies on electrocatalytic reactions (Ref. [33, 51, 52]). Given that redox potentials of the newly synthesized complexes (Fe-Py, Fe-PPh and Fe-PPy) are quite similar to the reported complex, Fe-Ph, the nature of the redox processes and the electronic structure of the reduced species are probably similar. Therefore, we have assigned the redox processes of the newly synthesized complexes to be Fe(III)/Fe(II), Fe(II)/Fe(I) and Fe(I)/Fe(0) according to the previous reports.

  2. It should be noted that the concentration of CO2 in solution can be an important factor to affect the reaction rate. In our experiments, CO2-saturated solutions were employed in all the electrochemical measurements under a CO2 atmosphere although the exact concentration of CO2 in the 1,2-diclorobenzene solutions was unknown.

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Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research (B) (No. 16H04125) (to S.M.), a Grant-in-Aid for Young Scientists (A) (No. 15H05480) (to M.K.), and a Grant-in-Aid for Challenging Exploratory Research (No. 26620160) (to S.M.) from the Japan Society for the Promotion of Science. This work was also supported by a Grant-in-Aid for Scientific Research on Innovative Areas “AnApple” (No. 15H00889) and ACT-C, JST.

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Authors and Affiliations

  1. Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi, 444-8787, Japan

    Yuki Okabe, Sze Koon Lee, Mio Kondo & Shigeyuki Masaoka

  2. Department of Structural Molecular Science, School of Physical Sciences, SOKENDAI (The Graduate University for Advanced Studies), Shonan Village, Hayama-cho, Kanagawa, 240-0193, Japan

    Yuki Okabe, Sze Koon Lee, Mio Kondo & Shigeyuki Masaoka

  3. Japan Science and Technology Agency (JST), ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

    Mio Kondo

  4. Research Center of Integrative Molecular Systems (CIMoS), Institute for Molecular Science, Nishigo-naka 38, Myodaiji, Okazaki, Aichi, 444-8585, Japan

    Mio Kondo & Shigeyuki Masaoka

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  1. Yuki Okabe
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  2. Sze Koon Lee
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Correspondence to Mio Kondo or Shigeyuki Masaoka.

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Okabe, Y., Lee, S.K., Kondo, M. et al. Syntheses and CO2 reduction activities of π-expanded/extended iron porphyrin complexes. J Biol Inorg Chem 22, 713–725 (2017). https://doi.org/10.1007/s00775-017-1438-3

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  • DOI: https://doi.org/10.1007/s00775-017-1438-3

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