title: Synthesis and properties of hybrid porphyrin tapes.
abstract: Hybrid porphyrin tapes 3 and 4, consisting of a mixture of 3,5-di-tert-butylphenyl-substituted donor-type Zn(II)-porphyrins and pentafluorophenyl-substituted acceptor-type Zn(II)-porphyrins, were prepared by a synthetic route involving cross-condensation reaction of a Ni(II)-porphyrinyldipyrromethane and pentafluorophenyldipyrromethane with pentafluorobenzaldehyde followed by appropriate demetalation, remetalation, and oxidative ring-closure reaction. The Ni(II)-substituted porphyrin tapes 5 (Ni-Zn-Ni) and 6 (Ni-H(2)-Ni) were also prepared through similar routes. The hybrid porphyrin tapes 3 and 4 are more soluble and more stable than normal porphyrin tapes 1 and 2 consisting of only donor-type Zn(II)-porphyrins. The solid-state and crystal packing structures of 3, 4, and 5 were elucidated by single-crystal X-ray diffraction analysis. Singly meso-meso-linked hybrid porphyrin arrays 12 and 14 exhibit redox potentials that roughly correspond to each constituent porphyrin segments, while the redox potentials of the hybrid porphyrin tapes 3 and 4 are positively shifted as a whole. The two-photon absorption (TPA) values of 1-6 were measured by using a wavelength-scanning open aperture Z-scan method and found to be 1900, 21,000, 2200, 27,000, 24,000, and 26,000 GM, respectively. These results illustrate an important effect of elongation of π-electron conjugation for the enhancement of TPA values. The hybrid porphyrin tapes show slightly larger TPA values than the parent ones.
authors: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
authors: Takayuki
authors: T
authors: Tanaka
authors: Byung Sun
authors: BS
authors: Lee
authors: Naoki
authors: N
authors: Aratani
authors: Min-Chul
authors: MC
authors: Yoon
authors: Dongho
authors: D
authors: Kim
authors: Atsuhiro
authors: A
authors: Osuka
mesh_terms: D018360:Crystallography, X-Ray; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D011166:Porphyrins; D009532:Nickel; D015032:Zinc