Assemblies of supramolecular porphyrin dimers in pentagonal and hexagonal arrays exhibiting light-harvesting antenna function

Fatin Hajjaj, Zin Seok Yoon, Min Chul Yoon, Jaehong Park, Akiharu Satake, Dongho Kim, Yoshiaki Kobuke

Research output: Contribution to journalArticle

131 Citations (Scopus)

Abstract

Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one.

Original languageEnglish
Pages (from-to)4612-4623
Number of pages12
JournalJournal of the American Chemical Society
Volume128
Issue number14
DOIs
Publication statusPublished - 2006 Apr 12

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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