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

doi:10.1039/c5sc04748j

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

26 Citations (Scopus)

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 language	English
Pages (from-to)	4059-4066
Number of pages	8
Journal	Chemical Science
Volume	7
Issue number	7
DOIs	https://doi.org/10.1039/c5sc04748j
Publication status	Published - 2016 Jul 1

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© 2016 The Royal Society of Chemistry.

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Chemistry(all)

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

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.",

author = "Norihito Fukui and Lee, {Seung Kyu} and Kenichi Kato and Daiki Shimizu and Takayuki Tanaka and Sangsu Lee and Hideki Yorimitsu and Dongho Kim and Atsuhiro Osuka",

note = "Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

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doi = "10.1039/c5sc04748j",

language = "English",

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T1 - Regioselective phenylene-fusion reactions of Ni(II)-porphyrins controlled by an electron-withdrawing

T2 - Meso -substituent

AU - Fukui, Norihito

AU - Lee, Seung Kyu

AU - Kato, Kenichi

AU - Shimizu, Daiki

AU - Tanaka, Takayuki

AU - Lee, Sangsu

AU - Yorimitsu, Hideki

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2016/7/1

Y1 - 2016/7/1

N2 - 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.

AB - 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.

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ER -

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

Abstract

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