From diacetylferrocene to 1,1′-ferrocenyldiimines: Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property

Ting Yu Lee, Pui Ren Chiang, Ming Chen Tsai, Che Yu Lin, Jui-Hsien Huang

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.

Original languageEnglish
Pages (from-to)102-109
Number of pages8
JournalJournal of Molecular Structure
Volume935
Issue number1-3
DOIs
Publication statusPublished - 2009 Oct 29

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Light absorption
Molecular structure
Structural analysis
Amines
Optical properties
Single crystals
Derivatives
X rays
Electrons
Oxidation-Reduction
4-nitrophenyl
ferrocene

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{b422700ee51447269f393189da374c6c,
title = "From diacetylferrocene to 1,1′-ferrocenyldiimines: Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property",
abstract = "A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.",
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From diacetylferrocene to 1,1′-ferrocenyldiimines : Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property. / Lee, Ting Yu; Chiang, Pui Ren; Tsai, Ming Chen; Lin, Che Yu; Huang, Jui-Hsien.

In: Journal of Molecular Structure, Vol. 935, No. 1-3, 29.10.2009, p. 102-109.

Research output: Contribution to journalArticle

TY - JOUR

T1 - From diacetylferrocene to 1,1′-ferrocenyldiimines

T2 - Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property

AU - Lee, Ting Yu

AU - Chiang, Pui Ren

AU - Tsai, Ming Chen

AU - Lin, Che Yu

AU - Huang, Jui-Hsien

PY - 2009/10/29

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N2 - A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.

AB - A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.

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