Large porphyrin squares from the self-assembly of meso-Triazole-Appended L-Shaped meso-meso-Linked ZnII-Triporphyrins: synthesis and efficient energy transfer

Chihiro Maeda*, Pyosang Kim, Sung Cho, Jong Kang Park, Jong Min Lim, Dongho Kim, Josh Vura-Weis, Michael R Wasielewski, Hiroshi Shinokubo, Atsuhiro Osuka

*Corresponding author for this work

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

meso-Triazolyl-appended ZnIIporphyrins were readily prepared by CuI-catalyzed 1, 3-dipolar cycloaddi-tion of benzyl azide to meso-ethynylat-ed ZnII-porphyrin (click chemistry). In noncoordinating CHCl3 solvent, spon-taneous assembly occurred to form tet-rameric array (3)2: from meso-meso-linked diporphyrins 3 1 and dodecameric porphyrin squares (4)4 and (5) 4 from the L-shaped meso-meso-linked tripor-phyrins 4 and 5. The structures of these assemblies were examined by 1H NMR spectra, absorption spectra, and their gel permeation chromatography (GPC) retention time. Furthermore, the struc-tures of the dodecameric porphyrin squares (4) 4 and (5)4 were probed by small- and wide-angle X-ray scattering (SAXS/WAXS) measurements in solu-tion using a synchrotron source. Excita-tion-energy migration processes in these assemblies were also investigated in detail by using both steady-state and time-resolved spectroscopic methods, which revealed efficient excited-energy transfer (EET) between the meso-meso-linked ZnII-porphyrin units that occurred with time constants of 1.5 ps-1 for(3)2 and 8.8ps-1 for (5)4.

Original languageEnglish (US)
Pages (from-to)5052-5061
Number of pages10
JournalChemistry - A European Journal
Volume16
Issue number17
DOIs
StatePublished - May 3 2010

Fingerprint

Triazoles
Porphyrins
Energy transfer
Self assembly
Azides
Gel permeation chromatography
X ray scattering
Synchrotrons
Absorption spectra
Nuclear magnetic resonance

Keywords

  • Energy transfer
  • Photo-synthesis
  • Porphyrinoids
  • Self-assembly
  • Triazoles

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Maeda, Chihiro ; Kim, Pyosang ; Cho, Sung ; Park, Jong Kang ; Lim, Jong Min ; Kim, Dongho ; Vura-Weis, Josh ; Wasielewski, Michael R ; Shinokubo, Hiroshi ; Osuka, Atsuhiro. / Large porphyrin squares from the self-assembly of meso-Triazole-Appended L-Shaped meso-meso-Linked ZnII-Triporphyrins : synthesis and efficient energy transfer. In: Chemistry - A European Journal. 2010 ; Vol. 16, No. 17. pp. 5052-5061.
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Large porphyrin squares from the self-assembly of meso-Triazole-Appended L-Shaped meso-meso-Linked ZnII-Triporphyrins : synthesis and efficient energy transfer. / Maeda, Chihiro; Kim, Pyosang; Cho, Sung; Park, Jong Kang; Lim, Jong Min; Kim, Dongho; Vura-Weis, Josh; Wasielewski, Michael R; Shinokubo, Hiroshi; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 16, No. 17, 03.05.2010, p. 5052-5061.

Research output: Contribution to journalArticle

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T2 - synthesis and efficient energy transfer

AU - Maeda, Chihiro

AU - Kim, Pyosang

AU - Cho, Sung

AU - Park, Jong Kang

AU - Lim, Jong Min

AU - Kim, Dongho

AU - Vura-Weis, Josh

AU - Wasielewski, Michael R

AU - Shinokubo, Hiroshi

AU - Osuka, Atsuhiro

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AB - meso-Triazolyl-appended ZnIIporphyrins were readily prepared by CuI-catalyzed 1, 3-dipolar cycloaddi-tion of benzyl azide to meso-ethynylat-ed ZnII-porphyrin (click chemistry). In noncoordinating CHCl3 solvent, spon-taneous assembly occurred to form tet-rameric array (3)2: from meso-meso-linked diporphyrins 3 1 and dodecameric porphyrin squares (4)4 and (5) 4 from the L-shaped meso-meso-linked tripor-phyrins 4 and 5. The structures of these assemblies were examined by 1H NMR spectra, absorption spectra, and their gel permeation chromatography (GPC) retention time. Furthermore, the struc-tures of the dodecameric porphyrin squares (4) 4 and (5)4 were probed by small- and wide-angle X-ray scattering (SAXS/WAXS) measurements in solu-tion using a synchrotron source. Excita-tion-energy migration processes in these assemblies were also investigated in detail by using both steady-state and time-resolved spectroscopic methods, which revealed efficient excited-energy transfer (EET) between the meso-meso-linked ZnII-porphyrin units that occurred with time constants of 1.5 ps-1 for(3)2 and 8.8ps-1 for (5)4.

KW - Energy transfer

KW - Photo-synthesis

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KW - Self-assembly

KW - Triazoles

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