D<inf>3h</inf>-Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity

Yohei Ohkoda, Akane Asaishi, Tomoya Namiki, Tomoaki Hashimoto, Midori Yamada, Koichiro Shirai, Yuta Katagami, Tomoaki Sugaya, Makoto Tadokoro, Akiharu Satake

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The one-step synthesis of D<inf>3h</inf>-symmetric cyclic porphyrin trimers 1 composed of three 2,2′-[4,4′-bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel-mediated reductive coupling of meso-5,15-bis(6-chloro-4-methoxycarbonylpyrid-2-yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X-ray crystallography. Treatment of an η<sup>3</sup>-allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η<sup>3</sup>-allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. Separation anxiety: Chromatography on a cyanopropyl-modified column supplied a cyclic porphyrin trimer efficiently from a mixture of acyclic and cyclic oligomers (see scheme; cod=1,5-cyclooctadiene, bpy=2,2′-bipyridyl). Treatment of an η<sup>3</sup>-allylpalladium complex with the cyclic trimer gives a tris(palladium) complex, which indicates that the cyclic trimer is a versatile macrocyclic ligand for multicofacial multimetallic complexes.

Original languageEnglish
Pages (from-to)11745-11756
Number of pages12
JournalChemistry - A European Journal
Volume21
Issue number33
DOIs
Publication statusPublished - 2015 Aug 1
Externally publishedYes

Fingerprint

2,2'-Dipyridyl
Porphyrins
Ligands
Palladium
Oligomers
X ray crystallography
Silica Gel
Silica gel
Chromatography
Nickel
Structural analysis
Nuclear magnetic resonance spectroscopy

Keywords

  • column chromatography
  • macrocycles
  • multinuclear complex
  • porphyrinoids
  • synthesis design

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

D<inf>3h</inf>-Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity. / Ohkoda, Yohei; Asaishi, Akane; Namiki, Tomoya; Hashimoto, Tomoaki; Yamada, Midori; Shirai, Koichiro; Katagami, Yuta; Sugaya, Tomoaki; Tadokoro, Makoto; Satake, Akiharu.

In: Chemistry - A European Journal, Vol. 21, No. 33, 01.08.2015, p. 11745-11756.

Research output: Contribution to journalArticle

Ohkoda, Y, Asaishi, A, Namiki, T, Hashimoto, T, Yamada, M, Shirai, K, Katagami, Y, Sugaya, T, Tadokoro, M & Satake, A 2015, 'D<inf>3h</inf>-Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity', Chemistry - A European Journal, vol. 21, no. 33, pp. 11745-11756. https://doi.org/10.1002/chem.201501854
Ohkoda, Yohei ; Asaishi, Akane ; Namiki, Tomoya ; Hashimoto, Tomoaki ; Yamada, Midori ; Shirai, Koichiro ; Katagami, Yuta ; Sugaya, Tomoaki ; Tadokoro, Makoto ; Satake, Akiharu. / D<inf>3h</inf>-Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity. In: Chemistry - A European Journal. 2015 ; Vol. 21, No. 33. pp. 11745-11756.
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AU - Hashimoto, Tomoaki

AU - Yamada, Midori

AU - Shirai, Koichiro

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