On the molecular recognition and associations between electrically conducting polyaniline and solvents

Olli Ikkala, Lars-Olof Pietilä, Lisbeth Ahjopalo, Heidi Österholm, Pentti Passiniemi

Research output: Contribution to journalArticleScientificpeer-review

153 Citations (Scopus)

Abstract

The specific interactions between sulphonic acid protonated polyaniline (PANI) and solvents are here studied both by the semiempirical AM1 method and experimentally.
Phenolic solvents are shown to have a relatively large interaction with the sulphonate anions of the counterions and with the amines in PANI. In addition, a properly functionalized counterion may form cyclic associations provided that there is a steric match between the molecules concerned.
This concept is called molecular recognition and it is a novel concept in the context of PANI. For example, the carbonyl group in (±)‐10‐camphor sulphonic acid (CSA) can form a hydrogen bond to the hydroxyl group of m‐cresol, whereby the phenyl ring becomes coplanar with one of the PANI rings thus enabling enhanced van der Waals interaction. This additional specific interaction agrees with our observed increased solubility with CSA doped PANI in m‐cresol, compared to its solubility in dimethyl sulphoxide or chloroform, or to tosylene sulphonic acid doped PANI in m‐cresol.
The above cyclic associations are suggested for dilute solutions and for the amorphous domains of solid films. In the latter case, they provide a potential mechanism to yield planar conformation in the crystalline domains: during the evaporation of m‐cresol, stacking to crystal structure may twist the rings due to the planar m‐cresol molecules on top of PANI rings. This is in agreement with the observed high conductivity.
The present results indicate that computational methods combined with the concept of molecular recognition may open new possibilities to tailor the rigidities and solubilities of macromolecules.
Original languageEnglish
Article number9855
JournalJournal of Chemical Physics
Volume103
Issue number22
DOIs
Publication statusPublished - 1995
MoE publication typeA1 Journal article-refereed

Fingerprint

Molecular recognition
sulfonic acid
conduction
solubility
rings
Sulfonic Acids
interactions
Solubility
sulfonates
chloroform
macromolecules
rigidity
molecules
amines
evaporation
Molecules
hydrogen bonds
anions
conductivity
crystal structure

Cite this

Ikkala, Olli ; Pietilä, Lars-Olof ; Ahjopalo, Lisbeth ; Österholm, Heidi ; Passiniemi, Pentti. / On the molecular recognition and associations between electrically conducting polyaniline and solvents. In: Journal of Chemical Physics. 1995 ; Vol. 103, No. 22.
@article{f167aab64fcb4081bdc05617658693cb,
title = "On the molecular recognition and associations between electrically conducting polyaniline and solvents",
abstract = "The specific interactions between sulphonic acid protonated polyaniline (PANI) and solvents are here studied both by the semiempirical AM1 method and experimentally. Phenolic solvents are shown to have a relatively large interaction with the sulphonate anions of the counterions and with the amines in PANI. In addition, a properly functionalized counterion may form cyclic associations provided that there is a steric match between the molecules concerned. This concept is called molecular recognition and it is a novel concept in the context of PANI. For example, the carbonyl group in (±)‐10‐camphor sulphonic acid (CSA) can form a hydrogen bond to the hydroxyl group of m‐cresol, whereby the phenyl ring becomes coplanar with one of the PANI rings thus enabling enhanced van der Waals interaction. This additional specific interaction agrees with our observed increased solubility with CSA doped PANI in m‐cresol, compared to its solubility in dimethyl sulphoxide or chloroform, or to tosylene sulphonic acid doped PANI in m‐cresol. The above cyclic associations are suggested for dilute solutions and for the amorphous domains of solid films. In the latter case, they provide a potential mechanism to yield planar conformation in the crystalline domains: during the evaporation of m‐cresol, stacking to crystal structure may twist the rings due to the planar m‐cresol molecules on top of PANI rings. This is in agreement with the observed high conductivity. The present results indicate that computational methods combined with the concept of molecular recognition may open new possibilities to tailor the rigidities and solubilities of macromolecules.",
author = "Olli Ikkala and Lars-Olof Pietil{\"a} and Lisbeth Ahjopalo and Heidi {\"O}sterholm and Pentti Passiniemi",
year = "1995",
doi = "10.1063/1.469952",
language = "English",
volume = "103",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics AIP",
number = "22",

}

On the molecular recognition and associations between electrically conducting polyaniline and solvents. / Ikkala, Olli; Pietilä, Lars-Olof; Ahjopalo, Lisbeth; Österholm, Heidi; Passiniemi, Pentti.

In: Journal of Chemical Physics, Vol. 103, No. 22, 9855, 1995.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - On the molecular recognition and associations between electrically conducting polyaniline and solvents

AU - Ikkala, Olli

AU - Pietilä, Lars-Olof

AU - Ahjopalo, Lisbeth

AU - Österholm, Heidi

AU - Passiniemi, Pentti

PY - 1995

Y1 - 1995

N2 - The specific interactions between sulphonic acid protonated polyaniline (PANI) and solvents are here studied both by the semiempirical AM1 method and experimentally. Phenolic solvents are shown to have a relatively large interaction with the sulphonate anions of the counterions and with the amines in PANI. In addition, a properly functionalized counterion may form cyclic associations provided that there is a steric match between the molecules concerned. This concept is called molecular recognition and it is a novel concept in the context of PANI. For example, the carbonyl group in (±)‐10‐camphor sulphonic acid (CSA) can form a hydrogen bond to the hydroxyl group of m‐cresol, whereby the phenyl ring becomes coplanar with one of the PANI rings thus enabling enhanced van der Waals interaction. This additional specific interaction agrees with our observed increased solubility with CSA doped PANI in m‐cresol, compared to its solubility in dimethyl sulphoxide or chloroform, or to tosylene sulphonic acid doped PANI in m‐cresol. The above cyclic associations are suggested for dilute solutions and for the amorphous domains of solid films. In the latter case, they provide a potential mechanism to yield planar conformation in the crystalline domains: during the evaporation of m‐cresol, stacking to crystal structure may twist the rings due to the planar m‐cresol molecules on top of PANI rings. This is in agreement with the observed high conductivity. The present results indicate that computational methods combined with the concept of molecular recognition may open new possibilities to tailor the rigidities and solubilities of macromolecules.

AB - The specific interactions between sulphonic acid protonated polyaniline (PANI) and solvents are here studied both by the semiempirical AM1 method and experimentally. Phenolic solvents are shown to have a relatively large interaction with the sulphonate anions of the counterions and with the amines in PANI. In addition, a properly functionalized counterion may form cyclic associations provided that there is a steric match between the molecules concerned. This concept is called molecular recognition and it is a novel concept in the context of PANI. For example, the carbonyl group in (±)‐10‐camphor sulphonic acid (CSA) can form a hydrogen bond to the hydroxyl group of m‐cresol, whereby the phenyl ring becomes coplanar with one of the PANI rings thus enabling enhanced van der Waals interaction. This additional specific interaction agrees with our observed increased solubility with CSA doped PANI in m‐cresol, compared to its solubility in dimethyl sulphoxide or chloroform, or to tosylene sulphonic acid doped PANI in m‐cresol. The above cyclic associations are suggested for dilute solutions and for the amorphous domains of solid films. In the latter case, they provide a potential mechanism to yield planar conformation in the crystalline domains: during the evaporation of m‐cresol, stacking to crystal structure may twist the rings due to the planar m‐cresol molecules on top of PANI rings. This is in agreement with the observed high conductivity. The present results indicate that computational methods combined with the concept of molecular recognition may open new possibilities to tailor the rigidities and solubilities of macromolecules.

U2 - 10.1063/1.469952

DO - 10.1063/1.469952

M3 - Article

VL - 103

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 22

M1 - 9855

ER -