Giant Porphyrin Wheels with Large Electronic Coupling as Models of Light-Harvesting Photosynthetic Antenna

• Published in: Chemistry : a European journal 2006-02, Vol.12 (5), p.1319-1327
• Main Authors: Hori, Takaaki, Aratani, Naoki, Takagi, Akihiko, Matsumoto, Takuya, Kawai, Tomoji, Yoon, Min-Chul, Yoon, Zin Seok, Cho, Sung, Kim, Dongho, Osuka, Atsuhiro
• Format: Article
• Language: English
• Subjects: energy transfer; Light-Harvesting Protein Complexes - chemistry; Light-Harvesting Protein Complexes - ultrastructure; Metalloporphyrins - chemical synthesis; Metalloporphyrins - chemistry; Microscopy, Scanning Tunneling; Models, Molecular; nanostructures; oligomerization; photosynthetic antenna; porphyrinoids; Porphyrins - chemical synthesis; Porphyrins - chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200501373

Starting from a 1,3‐phenylene‐linked diporphyrin zinc(II) complex 2ZA, repeated stepwise AgI‐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 1H 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. Record breakers! The present report describes what is clearly the world record holder for porphyrin‐based ring systems with the largest discrete porphyrin wheel (see figure). It could well be the record for any ring of purely synthetic origin. This could be important for the construction of porphyrin arrays with ample electronic interactions as a model of light‐harvesting antenna.