title: Giant porphyrin wheels with large electronic coupling as models of light-harvesting photosynthetic antenna.
abstract: 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 (1x10(-6) M) gave porphyrin ring C12ZA with a diameter of approximately 35 A 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 A 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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, and Core Research for Evolutional Science and Technology, Japan Science and Technology Agency, Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Takaaki
authors.initials: T
authors.lastname: Hori
authors.forename: Naoki
authors.initials: N
authors.lastname: Aratani
authors.forename: Akihiko
authors.initials: A
authors.lastname: Takagi
authors.forename: Takuya
authors.initials: T
authors.lastname: Matsumoto
authors.forename: Tomoji
authors.initials: T
authors.lastname: Kawai
authors.forename: Min-Chul
authors.initials: MC
authors.lastname: Yoon
authors.forename: Zin Seok
authors.initials: ZS
authors.lastname: Yoon
authors.forename: Sung
authors.initials: S
authors.lastname: Cho
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
mesh_terms: D045342:Light-Harvesting Protein Complexes / Q000737:chemistry* / Q000648:ultrastructure; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D016252:Microscopy, Scanning Tunneling; D008958:Models, Molecular; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: C509026:C12ZA porphyrin; C509027:C24ZB porphyrin; D045342:Light-Harvesting Protein Complexes; D008665:Metalloporphyrins; D011166:Porphyrins