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Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage.
Chemistry
July 2022
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
Invited for the cover of this issue are Kentaro Tanaka at Nagoya University and co-workers. The image depicts the importance of the flexibility of bridging alkyl chains in a molecular conjugate to pack the components closely to generate efficient molecular communication. Read the full text of the article at 10.
View Article and Find Full Text PDFSignificant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage.
Chemistry
July 2022
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility.
View Article and Find Full Text PDFSite-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer.
Chemistry
March 2019
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 , which is connected through a fourfold rotaxane, was prepared.
View Article and Find Full Text PDFProgrammable arrangement of metal ions in a cofacially stacked assembly of porphyrinoids toward molecular tags.
Dalton Trans
May 2018
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
Cofacial assemblies of metalloporphyrinoids represent a fascinating platform for the fabrication of novel functional molecular assemblies based on π-π, d-d, and d-π interactions between components. In this paper, we present a novel synthetic strategy for the programmable arrangement of different metal ions inside a cofacially stacked trimer of porphyrinoids. A combination of two different assemblies was utilized for our purpose: a tetracationic fourfold rotaxane heterodimer between a porphyrin with four alkylammonium chains and a phthalocyanine bearing four peripheral crown ethers, and a stacked assembly between the fourfold rotaxane heterodimer and an additional tetraanionic porphyrin.
View Article and Find Full Text PDFOxygen Reduction to Water by a Cofacial Dimer of Iron(III)-Porphyrin and Iron(III)-Phthalocyanine Linked through a Highly Flexible Fourfold Rotaxane.
Chemistry
June 2017
Department of Chemistry, Faculty of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
A μ-oxo-dinuclear iron complex of a supramolecular porphyrin-phthalocyanine conjugate was synthesized and its catalytic electrochemical oxygen reduction properties were investigated. In the conjugate, porphyrin and phthalocyanine units were connected to form a cofacial dimeric structure through a flexible fourfold rotaxane linkage, which was advantageous for accommodating small substrates between the iron centers. The conjugate showed efficient catalytic properties, at more positive potentials than those of other reported dinuclear porphyrinoid iron complexes, to selectively afford water through a four-electron reduction process.
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