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Giant Porphyrin Wheels with Large Electronic Coupling as Models of Light‐Harvesting Photosynthetic Antenna
Author(s) -
Hori Takaaki,
Aratani Naoki,
Takagi Akihiko,
Matsumoto Takuya,
Kawai Tomoji,
Yoon MinChul,
Yoon Zin Seok,
Cho Sung,
Kim Dongho,
Osuka Atsuhiro
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200501373
Subject(s) - porphyrin , spectroscopy , photochemistry , phenylene , intramolecular force , scanning tunneling microscope , chemistry , desorption , materials science , analytical chemistry (journal) , nanotechnology , stereochemistry , organic chemistry , physics , adsorption , quantum mechanics , polymer
Starting from a 1,3‐phenylene‐linked diporphyrin zinc( II ) complex 2ZA , repeated stepwise Ag I ‐promoted coupling reactions provided linear oligomers 4ZA , 6ZA , 8ZA , and 12ZA . The intramolecular cyclization reaction of 12ZA under dilute conditions (1×10 −6 M ) gave porphyrin ring C12ZA with a diameter of approximately 35 Å in 60 % yield. This synthetic strategy has been applied to a 1,3‐phenylene‐linked tetraporphyrin 4ZB to provide 8ZB , 12ZB , 16ZB , 24ZB , and 32ZB . The intramolecular coupling reaction of 24ZB gave a larger 24‐mer porphyrin ring C24ZB with a diameter of approximately 70 Å in 34 % yield. These two large porphyrin rings were characterized by means of 1 H NMR spectroscopy, matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectroscopy, UV‐visible spectroscopy, gel permeation chromatography (GPC) analysis, and scanning tunneling microscopy (STM) techniques. The STM images of C12ZA reveal largely circular structures, whereas those of C24ZB exhibit mostly ellipsoidal shapes, indicating more conformational flexibility of C24ZB . Similar to the case of C12ZA , the efficient excitation energy transfer along the ring has been confirmed for C24ZB by using the time‐correlated single‐photon counting (TCSPC) and picosecond transient absorption anisotropy (TAA) measurements, and occurs with a rate of (35 ps) −1 for energy hops between neighboring tetraporphyrin subunits. Collectively, the present work provides an important step for the construction of large cyclic‐arranged porphyrin arrays with ample electronic interactions as a model of light‐harvesting antenna.