N,N-Butyl-decamethylferrocenyl-amine reactivity at liquid vertical bar liquid interfaces: electrochemically driven anion transfer vs. pH driven proton transfer

Andrew M Kelly, Najoua Katif, Tony James, Frank Marken

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We have developed a permethylated ferrocene redox system with a butylamine substituent for application in liquid vertical bar liquid ion sensors. The steric hindrance associated with the methyl groups results in an electrochemical system where the ferricenium derivative is chemically inert and the redox system remains chemically reversible, even for applications in aqueous or biphasic media. N,N-Butyl-decamethylferrocenyl-amine is soluble in hydrophobic organic solvents, such as 4-(3-phenylpropyl) pyridine (PPP) and N-octyl-pyrrolidone (NOP), and is employed here under "microphase'' conditions, deposited in the form of microdroplets onto an electrode and immersed in aqueous buffer solutions. It is shown that under these conditions, electron transfer and proton transfer are only weakly coupled, and that anion transfer dominates the microphase redox process over the entire pH range. The corresponding biphasic Pourbaix diagram is discussed.
Original languageEnglish
Pages (from-to)1261-1265
Number of pages5
JournalNew Journal of Chemistry
Volume34
Issue number7
DOIs
Publication statusPublished - Jul 2010

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Proton transfer
Amines
Anions
Negative ions
Liquids
Butylamines
Pyrrolidinones
Pyridine
Organic solvents
Buffers
Ions
Derivatives
Electrodes
Electrons
Sensors
Oxidation-Reduction

Cite this

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title = "N,N-Butyl-decamethylferrocenyl-amine reactivity at liquid vertical bar liquid interfaces: electrochemically driven anion transfer vs. pH driven proton transfer",
abstract = "We have developed a permethylated ferrocene redox system with a butylamine substituent for application in liquid vertical bar liquid ion sensors. The steric hindrance associated with the methyl groups results in an electrochemical system where the ferricenium derivative is chemically inert and the redox system remains chemically reversible, even for applications in aqueous or biphasic media. N,N-Butyl-decamethylferrocenyl-amine is soluble in hydrophobic organic solvents, such as 4-(3-phenylpropyl) pyridine (PPP) and N-octyl-pyrrolidone (NOP), and is employed here under {"}microphase'' conditions, deposited in the form of microdroplets onto an electrode and immersed in aqueous buffer solutions. It is shown that under these conditions, electron transfer and proton transfer are only weakly coupled, and that anion transfer dominates the microphase redox process over the entire pH range. The corresponding biphasic Pourbaix diagram is discussed.",
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TY - JOUR

T1 - N,N-Butyl-decamethylferrocenyl-amine reactivity at liquid vertical bar liquid interfaces: electrochemically driven anion transfer vs. pH driven proton transfer

AU - Kelly, Andrew M

AU - Katif, Najoua

AU - James, Tony

AU - Marken, Frank

PY - 2010/7

Y1 - 2010/7

N2 - We have developed a permethylated ferrocene redox system with a butylamine substituent for application in liquid vertical bar liquid ion sensors. The steric hindrance associated with the methyl groups results in an electrochemical system where the ferricenium derivative is chemically inert and the redox system remains chemically reversible, even for applications in aqueous or biphasic media. N,N-Butyl-decamethylferrocenyl-amine is soluble in hydrophobic organic solvents, such as 4-(3-phenylpropyl) pyridine (PPP) and N-octyl-pyrrolidone (NOP), and is employed here under "microphase'' conditions, deposited in the form of microdroplets onto an electrode and immersed in aqueous buffer solutions. It is shown that under these conditions, electron transfer and proton transfer are only weakly coupled, and that anion transfer dominates the microphase redox process over the entire pH range. The corresponding biphasic Pourbaix diagram is discussed.

AB - We have developed a permethylated ferrocene redox system with a butylamine substituent for application in liquid vertical bar liquid ion sensors. The steric hindrance associated with the methyl groups results in an electrochemical system where the ferricenium derivative is chemically inert and the redox system remains chemically reversible, even for applications in aqueous or biphasic media. N,N-Butyl-decamethylferrocenyl-amine is soluble in hydrophobic organic solvents, such as 4-(3-phenylpropyl) pyridine (PPP) and N-octyl-pyrrolidone (NOP), and is employed here under "microphase'' conditions, deposited in the form of microdroplets onto an electrode and immersed in aqueous buffer solutions. It is shown that under these conditions, electron transfer and proton transfer are only weakly coupled, and that anion transfer dominates the microphase redox process over the entire pH range. The corresponding biphasic Pourbaix diagram is discussed.

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UR - http://dx.doi.org/10.1039/c0nj00166j

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JF - New Journal of Chemistry

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