Regioselective phenylene-fusion reactions of Ni(II)-porphyrins controlled by an electron-withdrawing: Meso -substituent

Norihito Fukui, Seung Kyu Lee, Kenichi Kato, Daiki Shimizu, Takayuki Tanaka, Sangsu Lee, Hideki Yorimitsu, Dongho Kim, Atsuhiro Osuka

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Abstract

Oxidation of 10,15,20-triaryl Ni(ii)-porphyrins bearing an electron-withdrawing substituent at the 5-position with DDQ and FeCl3 gave 10,12- and 18,20-doubly phenylene-fused Ni(ii)-porphyrins regioselectively. A doubly phenylene-fused meso-chloro porphyrin thus prepared was reductively coupled to give a meso-meso linked dimer, which was further converted to a quadruply phenylene-fused meso-meso, β-β, β-β triply linked Zn(ii)-diporphyrin via inner-metal exchange followed by oxidation with DDQ and Sc(OTf)3. As compared to the usual meso-meso, β-β, β-β triply linked Zn(ii)-diporphyrin, this π-extended porphyrin dyad exhibits a smaller HOMO-LUMO gap and a larger two-photon absorption cross-section.

Original languageEnglish
Pages (from-to)4059-4066
Number of pages8
JournalChemical Science
Volume7
Issue number7
DOIs
Publication statusPublished - 2016 Jul 1

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All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Fukui, N., Lee, S. K., Kato, K., Shimizu, D., Tanaka, T., Lee, S., Yorimitsu, H., Kim, D., & Osuka, A. (2016). Regioselective phenylene-fusion reactions of Ni(II)-porphyrins controlled by an electron-withdrawing: Meso -substituent. Chemical Science, 7(7), 4059-4066. https://doi.org/10.1039/c5sc04748j