Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety

Hideaki Takashima; Yusuke Inagaki; Hiroyuki Momma; Eunsang Kwon; Kentaro Yamaguchi; Wataru Setaka

doi:10.1021/acs.organomet.8b00154

Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety

Hideaki Takashima, Yusuke Inagaki, Hiroyuki Momma, Eunsang Kwon, Kentaro Yamaguchi, Wataru Setaka

SCI - Research and Analytical Center for Giant Molecules

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

Abstract

The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E_1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E_1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.

Original language	English
Pages (from-to)	1501-1506
Number of pages	6
Journal	Organometallics
Volume	37
Issue number	9
DOIs	https://doi.org/10.1021/acs.organomet.8b00154
Publication status	Published - 2018 May 14

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety",

abstract = "The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.",

author = "Hideaki Takashima and Yusuke Inagaki and Hiroyuki Momma and Eunsang Kwon and Kentaro Yamaguchi and Wataru Setaka",

note = "Funding Information: This work was supported by a JSPS Grant-in-Aid for Scientific Research on Innovation Areas “stimuli-responsive chemical species” (15H00955), Scientific Research (B) (25288042), and Iketani Science and Technology Foundation (0291033-A). Funding Information: This work was supported by a JSPS Grant-in-Aid for Scientific Research on Innovation Areas stimuli-responsive chemical species (15H00955), Scientific Research (B) (25288042), and Iketani Science and Technology Foundation (0291033-A). Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

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AU - Momma, Hiroyuki

AU - Kwon, Eunsang

AU - Yamaguchi, Kentaro

AU - Setaka, Wataru

N1 - Funding Information: This work was supported by a JSPS Grant-in-Aid for Scientific Research on Innovation Areas “stimuli-responsive chemical species” (15H00955), Scientific Research (B) (25288042), and Iketani Science and Technology Foundation (0291033-A). Funding Information: This work was supported by a JSPS Grant-in-Aid for Scientific Research on Innovation Areas stimuli-responsive chemical species (15H00955), Scientific Research (B) (25288042), and Iketani Science and Technology Foundation (0291033-A). Publisher Copyright: Copyright © 2018 American Chemical Society.

PY - 2018/5/14

Y1 - 2018/5/14

N2 - The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.

AB - The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.

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Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety

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