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Excitation-energy migration in self-assembled cyclic zinc(II)-porphyrin arrays: a close mimicry of a natural light-harvesting system
Authors:Hwang In-Wook  Park Mira  Ahn Tae Kyu  Yoon Zin Seok  Ko Dah Mee  Kim Dongho  Ito Fuyuki  Ishibashi Yukihide  Khan Sazzadur R  Nagasawa Yutaka  Miyasaka Hiroshi  Ikeda Chusaku  Takahashi Ryoichi  Ogawa Kazuya  Satake Akiharu  Kobuke Yoshiaki
Institution:Center for Ultrafast Optical Characteristics Control and Department of Chemistry, Yonsei University, Seoul, Korea.
Abstract:The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes.
Keywords:energy transfer  femtosecond transient absorption  fluorescence spectroscopy  polarization anisotropy  porphyrinoids
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