Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication

Naoki Aratani, Akihiko Takagi, Yoshiki Yanagawa, Takuya Matsumoto, Tomoji Kawai, Zin Seok Yoon, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

89 Citations (Scopus)

Abstract

On the basis of the AgI-promoted coupling reaction of zinc(II)-5,15-bis(3,5-dioctyloxyphenyl)porphyrin Z1, chain elongation has been attempted by using a stepwise doubling approach, which provides Z2, Z4, Z8, Z16, Z32, Z64, Z128, Z256, Z384, and Z512. The porphyrin arrays up to Z128 are sufficiently soluble in CHCl3 and THF despite their very long molecular lengths and rodlike structures, while the arrays over Z128 show a significant drop in solubility and stability. The discrete porphyrin arrays thus isolated were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV/Vis spectroscopy, gel-permeation chromatography (GPC), cyclic voltammetry (CV), single-crystal X-ray crystallography, scanning tunneling microscopy (STM), and atomic force microscopy (AFM). Contrary to expected linear conformations of the arrays Z n (where n is the number of porphyrins), the single molecular images of Z128, Z256, and Z512 revealed largely bent structures; this finding indicates the substantial conformational flexibility of Zn. We also exploited an effective synthetic route by means of which Zn can be fabricated with a thiol-protected aryl group to provide ZnS2 through ZnBr2, by bromination with N-bromosuccinimide and subsequent Pd-catalyzed Suzuki-Miyaura arylation. Finally, the reaction of Z256 provided Z512, Z768, and Z1024. Collectively, this work provides an important milestone in the preparation of sub-microscale discrete organic molecules and the fabrication of molecular-based materials, hence significantly contributing to device applications.

Original languageEnglish
Pages (from-to)3389-3404
Number of pages16
JournalChemistry - A European Journal
Volume11
Issue number11
DOIs
Publication statusPublished - 2005 May 20

Fingerprint

Porphyrins
Fabrication
Bromosuccinimide
X ray crystallography
Gel permeation chromatography
Scanning tunneling microscopy
Ultraviolet spectroscopy
Sulfhydryl Compounds
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Ionization
Mass spectrometry
Conformations
Zinc
Elongation
Atomic force microscopy
Desorption
Solubility
Single crystals
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Aratani, N., Takagi, A., Yanagawa, Y., Matsumoto, T., Kawai, T., Yoon, Z. S., ... Osuka, A. (2005). Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication. Chemistry - A European Journal, 11(11), 3389-3404. https://doi.org/10.1002/chem.200401306
Aratani, Naoki ; Takagi, Akihiko ; Yanagawa, Yoshiki ; Matsumoto, Takuya ; Kawai, Tomoji ; Yoon, Zin Seok ; Kim, Dongho ; Osuka, Atsuhiro. / Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication. In: Chemistry - A European Journal. 2005 ; Vol. 11, No. 11. pp. 3389-3404.
@article{4ba1db1999774a1f926790264dc6e9db,
title = "Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication",
abstract = "On the basis of the AgI-promoted coupling reaction of zinc(II)-5,15-bis(3,5-dioctyloxyphenyl)porphyrin Z1, chain elongation has been attempted by using a stepwise doubling approach, which provides Z2, Z4, Z8, Z16, Z32, Z64, Z128, Z256, Z384, and Z512. The porphyrin arrays up to Z128 are sufficiently soluble in CHCl3 and THF despite their very long molecular lengths and rodlike structures, while the arrays over Z128 show a significant drop in solubility and stability. The discrete porphyrin arrays thus isolated were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV/Vis spectroscopy, gel-permeation chromatography (GPC), cyclic voltammetry (CV), single-crystal X-ray crystallography, scanning tunneling microscopy (STM), and atomic force microscopy (AFM). Contrary to expected linear conformations of the arrays Z n (where n is the number of porphyrins), the single molecular images of Z128, Z256, and Z512 revealed largely bent structures; this finding indicates the substantial conformational flexibility of Zn. We also exploited an effective synthetic route by means of which Zn can be fabricated with a thiol-protected aryl group to provide ZnS2 through ZnBr2, by bromination with N-bromosuccinimide and subsequent Pd-catalyzed Suzuki-Miyaura arylation. Finally, the reaction of Z256 provided Z512, Z768, and Z1024. Collectively, this work provides an important milestone in the preparation of sub-microscale discrete organic molecules and the fabrication of molecular-based materials, hence significantly contributing to device applications.",
author = "Naoki Aratani and Akihiko Takagi and Yoshiki Yanagawa and Takuya Matsumoto and Tomoji Kawai and Yoon, {Zin Seok} and Dongho Kim and Atsuhiro Osuka",
year = "2005",
month = "5",
day = "20",
doi = "10.1002/chem.200401306",
language = "English",
volume = "11",
pages = "3389--3404",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "11",

}

Aratani, N, Takagi, A, Yanagawa, Y, Matsumoto, T, Kawai, T, Yoon, ZS, Kim, D & Osuka, A 2005, 'Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication', Chemistry - A European Journal, vol. 11, no. 11, pp. 3389-3404. https://doi.org/10.1002/chem.200401306

Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication. / Aratani, Naoki; Takagi, Akihiko; Yanagawa, Yoshiki; Matsumoto, Takuya; Kawai, Tomoji; Yoon, Zin Seok; Kim, Dongho; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 11, No. 11, 20.05.2005, p. 3389-3404.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication

AU - Aratani, Naoki

AU - Takagi, Akihiko

AU - Yanagawa, Yoshiki

AU - Matsumoto, Takuya

AU - Kawai, Tomoji

AU - Yoon, Zin Seok

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2005/5/20

Y1 - 2005/5/20

N2 - On the basis of the AgI-promoted coupling reaction of zinc(II)-5,15-bis(3,5-dioctyloxyphenyl)porphyrin Z1, chain elongation has been attempted by using a stepwise doubling approach, which provides Z2, Z4, Z8, Z16, Z32, Z64, Z128, Z256, Z384, and Z512. The porphyrin arrays up to Z128 are sufficiently soluble in CHCl3 and THF despite their very long molecular lengths and rodlike structures, while the arrays over Z128 show a significant drop in solubility and stability. The discrete porphyrin arrays thus isolated were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV/Vis spectroscopy, gel-permeation chromatography (GPC), cyclic voltammetry (CV), single-crystal X-ray crystallography, scanning tunneling microscopy (STM), and atomic force microscopy (AFM). Contrary to expected linear conformations of the arrays Z n (where n is the number of porphyrins), the single molecular images of Z128, Z256, and Z512 revealed largely bent structures; this finding indicates the substantial conformational flexibility of Zn. We also exploited an effective synthetic route by means of which Zn can be fabricated with a thiol-protected aryl group to provide ZnS2 through ZnBr2, by bromination with N-bromosuccinimide and subsequent Pd-catalyzed Suzuki-Miyaura arylation. Finally, the reaction of Z256 provided Z512, Z768, and Z1024. Collectively, this work provides an important milestone in the preparation of sub-microscale discrete organic molecules and the fabrication of molecular-based materials, hence significantly contributing to device applications.

AB - On the basis of the AgI-promoted coupling reaction of zinc(II)-5,15-bis(3,5-dioctyloxyphenyl)porphyrin Z1, chain elongation has been attempted by using a stepwise doubling approach, which provides Z2, Z4, Z8, Z16, Z32, Z64, Z128, Z256, Z384, and Z512. The porphyrin arrays up to Z128 are sufficiently soluble in CHCl3 and THF despite their very long molecular lengths and rodlike structures, while the arrays over Z128 show a significant drop in solubility and stability. The discrete porphyrin arrays thus isolated were characterized by means of 1H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV/Vis spectroscopy, gel-permeation chromatography (GPC), cyclic voltammetry (CV), single-crystal X-ray crystallography, scanning tunneling microscopy (STM), and atomic force microscopy (AFM). Contrary to expected linear conformations of the arrays Z n (where n is the number of porphyrins), the single molecular images of Z128, Z256, and Z512 revealed largely bent structures; this finding indicates the substantial conformational flexibility of Zn. We also exploited an effective synthetic route by means of which Zn can be fabricated with a thiol-protected aryl group to provide ZnS2 through ZnBr2, by bromination with N-bromosuccinimide and subsequent Pd-catalyzed Suzuki-Miyaura arylation. Finally, the reaction of Z256 provided Z512, Z768, and Z1024. Collectively, this work provides an important milestone in the preparation of sub-microscale discrete organic molecules and the fabrication of molecular-based materials, hence significantly contributing to device applications.

UR - http://www.scopus.com/inward/record.url?scp=19944388615&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=19944388615&partnerID=8YFLogxK

U2 - 10.1002/chem.200401306

DO - 10.1002/chem.200401306

M3 - Article

C2 - 15798970

AN - SCOPUS:19944388615

VL - 11

SP - 3389

EP - 3404

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 11

ER -