Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase

Evan L. Anderson, Nicole M. Gingery, Paul G. Boswell, Xin V. Chen, J. Rábai, Philippe Bühlmann

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Potentiometric selectivities show that in fluorous ion-selective electrode membranes the tetrabutylammonium ion binds to fluorophilic proton ionophores. For the ionophore bis[3-(perfluorooctyl)propyl](2,2,2-trifluoroethyl)amine, this type of interaction is confirmed by the effect of the ionophore on the ionic conductivity of perfluoro(perhydrophenanthrene) solutions of a fluorophilic NBu4+ salt. In this system, ion pairs, triple ions, and higher ionic aggregates dominate over single ions, and the ionophore increases the conductivity by favoring the formation of ion aggregates with a net charge. These observations are consistent with the formation of R3N+-C(R)-H···NR3 type hydrogen bonds between the nitrogen atom of the ionophore and the hydrogen atoms in the α position to the positively charged quaternary ammonium center of NBu4+. Similar interactions were observed in a number of crystalline phases. To date, observations of C-H···N type hydrogen bonds in liquid phases have been very few, and solution-phase N+-C-H···N type hydrogen bonds have not been reported previously. Interestingly, no interactions between NBu4+ and the more basic ionophore tridodecylamine were observed in conventional plasticized poly(vinyl chloride) membranes doped with the ionophore tridodecylamine, emphasizing the uniquely low polarity of fluorous phases.

Original languageEnglish
Pages (from-to)11239-11246
Number of pages8
JournalThe journal of physical chemistry. B
Volume120
Issue number43
Publication statusPublished - Nov 3 2016

Fingerprint

Ionophores
Hydrogen Bonding
Hydrogen bonds
Agglomeration
Ions
Hydrogen
hydrogen
hydrogen bonds
ions
Proton Ionophores
membranes
ion selective electrodes
Membranes
Vinyl Chloride
Ion-Selective Electrodes
interactions
Atoms
nitrogen atoms
ion currents
Ionic conductivity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Anderson, E. L., Gingery, N. M., Boswell, P. G., Chen, X. V., Rábai, J., & Bühlmann, P. (2016). Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase. The journal of physical chemistry. B, 120(43), 11239-11246.

Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase. / Anderson, Evan L.; Gingery, Nicole M.; Boswell, Paul G.; Chen, Xin V.; Rábai, J.; Bühlmann, Philippe.

In: The journal of physical chemistry. B, Vol. 120, No. 43, 03.11.2016, p. 11239-11246.

Research output: Contribution to journalArticle

Anderson, EL, Gingery, NM, Boswell, PG, Chen, XV, Rábai, J & Bühlmann, P 2016, 'Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase', The journal of physical chemistry. B, vol. 120, no. 43, pp. 11239-11246.
Anderson EL, Gingery NM, Boswell PG, Chen XV, Rábai J, Bühlmann P. Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase. The journal of physical chemistry. B. 2016 Nov 3;120(43):11239-11246.
Anderson, Evan L. ; Gingery, Nicole M. ; Boswell, Paul G. ; Chen, Xin V. ; Rábai, J. ; Bühlmann, Philippe. / Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase. In: The journal of physical chemistry. B. 2016 ; Vol. 120, No. 43. pp. 11239-11246.
@article{d5c88725f4224c469b43b9495759f1a8,
title = "Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase",
abstract = "Potentiometric selectivities show that in fluorous ion-selective electrode membranes the tetrabutylammonium ion binds to fluorophilic proton ionophores. For the ionophore bis[3-(perfluorooctyl)propyl](2,2,2-trifluoroethyl)amine, this type of interaction is confirmed by the effect of the ionophore on the ionic conductivity of perfluoro(perhydrophenanthrene) solutions of a fluorophilic NBu4+ salt. In this system, ion pairs, triple ions, and higher ionic aggregates dominate over single ions, and the ionophore increases the conductivity by favoring the formation of ion aggregates with a net charge. These observations are consistent with the formation of R3N+-C(R)-H···NR3 type hydrogen bonds between the nitrogen atom of the ionophore and the hydrogen atoms in the α position to the positively charged quaternary ammonium center of NBu4+. Similar interactions were observed in a number of crystalline phases. To date, observations of C-H···N type hydrogen bonds in liquid phases have been very few, and solution-phase N+-C-H···N type hydrogen bonds have not been reported previously. Interestingly, no interactions between NBu4+ and the more basic ionophore tridodecylamine were observed in conventional plasticized poly(vinyl chloride) membranes doped with the ionophore tridodecylamine, emphasizing the uniquely low polarity of fluorous phases.",
author = "Anderson, {Evan L.} and Gingery, {Nicole M.} and Boswell, {Paul G.} and Chen, {Xin V.} and J. R{\'a}bai and Philippe B{\"u}hlmann",
year = "2016",
month = "11",
day = "3",
language = "English",
volume = "120",
pages = "11239--11246",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "43",

}

TY - JOUR

T1 - Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase

AU - Anderson, Evan L.

AU - Gingery, Nicole M.

AU - Boswell, Paul G.

AU - Chen, Xin V.

AU - Rábai, J.

AU - Bühlmann, Philippe

PY - 2016/11/3

Y1 - 2016/11/3

N2 - Potentiometric selectivities show that in fluorous ion-selective electrode membranes the tetrabutylammonium ion binds to fluorophilic proton ionophores. For the ionophore bis[3-(perfluorooctyl)propyl](2,2,2-trifluoroethyl)amine, this type of interaction is confirmed by the effect of the ionophore on the ionic conductivity of perfluoro(perhydrophenanthrene) solutions of a fluorophilic NBu4+ salt. In this system, ion pairs, triple ions, and higher ionic aggregates dominate over single ions, and the ionophore increases the conductivity by favoring the formation of ion aggregates with a net charge. These observations are consistent with the formation of R3N+-C(R)-H···NR3 type hydrogen bonds between the nitrogen atom of the ionophore and the hydrogen atoms in the α position to the positively charged quaternary ammonium center of NBu4+. Similar interactions were observed in a number of crystalline phases. To date, observations of C-H···N type hydrogen bonds in liquid phases have been very few, and solution-phase N+-C-H···N type hydrogen bonds have not been reported previously. Interestingly, no interactions between NBu4+ and the more basic ionophore tridodecylamine were observed in conventional plasticized poly(vinyl chloride) membranes doped with the ionophore tridodecylamine, emphasizing the uniquely low polarity of fluorous phases.

AB - Potentiometric selectivities show that in fluorous ion-selective electrode membranes the tetrabutylammonium ion binds to fluorophilic proton ionophores. For the ionophore bis[3-(perfluorooctyl)propyl](2,2,2-trifluoroethyl)amine, this type of interaction is confirmed by the effect of the ionophore on the ionic conductivity of perfluoro(perhydrophenanthrene) solutions of a fluorophilic NBu4+ salt. In this system, ion pairs, triple ions, and higher ionic aggregates dominate over single ions, and the ionophore increases the conductivity by favoring the formation of ion aggregates with a net charge. These observations are consistent with the formation of R3N+-C(R)-H···NR3 type hydrogen bonds between the nitrogen atom of the ionophore and the hydrogen atoms in the α position to the positively charged quaternary ammonium center of NBu4+. Similar interactions were observed in a number of crystalline phases. To date, observations of C-H···N type hydrogen bonds in liquid phases have been very few, and solution-phase N+-C-H···N type hydrogen bonds have not been reported previously. Interestingly, no interactions between NBu4+ and the more basic ionophore tridodecylamine were observed in conventional plasticized poly(vinyl chloride) membranes doped with the ionophore tridodecylamine, emphasizing the uniquely low polarity of fluorous phases.

UR - http://www.scopus.com/inward/record.url?scp=85045392391&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85045392391&partnerID=8YFLogxK

M3 - Article

C2 - 27723332

AN - SCOPUS:85045392391

VL - 120

SP - 11239

EP - 11246

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 43

ER -