Synthesis of 7,8-dehydropurpurin dimers and their conversion into conformationally constrained β-to-β vinylene-bridged porphyrin dimers

Norihito Fukui, Hideki Yorimitsu, Jong Min Lim, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

7,8-Dehydropurpurin has attracted much attention owing to the dual 18π- and 20π-electron circuits in its macrocyclic conjugation. The two-fold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne furnished 7,8-dehydropurpurin dimers. The 8a,8a-linked dimer displays a red-shifted and enhanced absorption band in the NIR region and a small electrochemical HOMO-LUMO band gap as a consequence of efficient conjugation between the two coplanar 7,8-dehydropurpurin units. Treatment of this dimer with N-bromosuccinimide in chloroform and ethanol gave β-to-β vinylene-bridged porphyrin dimers. Owing to the highly constrained conformations, these dimers exhibit perturbed absorption spectra, small Stokes shifts, and high fluorescence quantum yields. Bridging the networks: 7,8-Dehydropurpurin dimers were synthesized by twofold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne. Treatment of this dimer with N-bromosuccinimide (NBS) in CHCl3 and ethanol gave the title porphyrin dimers, which exhibited well-conjugated electronic networks and constrained conformations.

Original languageEnglish
Pages (from-to)4395-4398
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number17
DOIs
Publication statusPublished - 2014 Apr 22

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Porphyrins
Dimers
Bromosuccinimide
Conformations
Absorption spectra
Ethanol
Quantum yield
Chloroform
Chlorine compounds
Energy gap
Fluorescence
Electrons
Networks (circuits)

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Synthesis of 7,8-dehydropurpurin dimers and their conversion into conformationally constrained β-to-β vinylene-bridged porphyrin dimers",
abstract = "7,8-Dehydropurpurin has attracted much attention owing to the dual 18π- and 20π-electron circuits in its macrocyclic conjugation. The two-fold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne furnished 7,8-dehydropurpurin dimers. The 8a,8a-linked dimer displays a red-shifted and enhanced absorption band in the NIR region and a small electrochemical HOMO-LUMO band gap as a consequence of efficient conjugation between the two coplanar 7,8-dehydropurpurin units. Treatment of this dimer with N-bromosuccinimide in chloroform and ethanol gave β-to-β vinylene-bridged porphyrin dimers. Owing to the highly constrained conformations, these dimers exhibit perturbed absorption spectra, small Stokes shifts, and high fluorescence quantum yields. Bridging the networks: 7,8-Dehydropurpurin dimers were synthesized by twofold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne. Treatment of this dimer with N-bromosuccinimide (NBS) in CHCl3 and ethanol gave the title porphyrin dimers, which exhibited well-conjugated electronic networks and constrained conformations.",
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Synthesis of 7,8-dehydropurpurin dimers and their conversion into conformationally constrained β-to-β vinylene-bridged porphyrin dimers. / Fukui, Norihito; Yorimitsu, Hideki; Lim, Jong Min; Kim, Dongho; Osuka, Atsuhiro.

In: Angewandte Chemie - International Edition, Vol. 53, No. 17, 22.04.2014, p. 4395-4398.

Research output: Contribution to journalArticle

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T1 - Synthesis of 7,8-dehydropurpurin dimers and their conversion into conformationally constrained β-to-β vinylene-bridged porphyrin dimers

AU - Fukui, Norihito

AU - Yorimitsu, Hideki

AU - Lim, Jong Min

AU - Kim, Dongho

AU - Osuka, Atsuhiro

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AB - 7,8-Dehydropurpurin has attracted much attention owing to the dual 18π- and 20π-electron circuits in its macrocyclic conjugation. The two-fold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne furnished 7,8-dehydropurpurin dimers. The 8a,8a-linked dimer displays a red-shifted and enhanced absorption band in the NIR region and a small electrochemical HOMO-LUMO band gap as a consequence of efficient conjugation between the two coplanar 7,8-dehydropurpurin units. Treatment of this dimer with N-bromosuccinimide in chloroform and ethanol gave β-to-β vinylene-bridged porphyrin dimers. Owing to the highly constrained conformations, these dimers exhibit perturbed absorption spectra, small Stokes shifts, and high fluorescence quantum yields. Bridging the networks: 7,8-Dehydropurpurin dimers were synthesized by twofold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne. Treatment of this dimer with N-bromosuccinimide (NBS) in CHCl3 and ethanol gave the title porphyrin dimers, which exhibited well-conjugated electronic networks and constrained conformations.

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