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

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

julkaisussa: Journal of Chemical Physics, Vuosikerta 103, Nro 22, 1995, s. 9855-9863.

Tutkimustuotos: Lehtiartikkelivertaisarvioitu

Harvard

Ikkala, OT, Pietilä, L-O, Ahjopalo, L, Österholm, H & Passiniemi, PJ 1995, 'On the molecular recognition and associations between electrically conducting polyaniline and solvents', Journal of Chemical Physics, Vuosikerta. 103, Nro 22, Sivut 9855-9863. https://doi.org/10.1063/1.469952

APA

Vancouver

Author

Ikkala, Olli T. ; Pietilä, Lars-Olof ; Ahjopalo, Lisbeth ; Österholm, Heidi ; Passiniemi, Pentti J. / On the molecular recognition and associations between electrically conducting polyaniline and solvents. Julkaisussa: Journal of Chemical Physics. 1995 ; Vuosikerta 103, Nro 22. Sivut 9855-9863.

Bibtex - Lataa

@article{0453cea8ff23439ab749f560fafe1a5a,
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.",
keywords = "electrically conducting polymer, hydrogen bonding, molecular recognition, phenyl-phenyl interaction, solvent, electrically conducting polymer, hydrogen bonding, molecular recognition, phenyl-phenyl interaction, solvent, electrically conducting polymer, hydrogen bonding, molecular recognition, phenyl-phenyl interaction, solvent",
author = "Ikkala, {Olli T.} and Lars-Olof Pietil{\"a} and Lisbeth Ahjopalo and Heidi {\"O}sterholm and Passiniemi, {Pentti J.}",
year = "1995",
doi = "10.1063/1.469952",
language = "English",
volume = "103",
pages = "9855--9863",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMERICAN INSTITUTE OF PHYSICS",
number = "22",

}

RIS - Lataa

TY - JOUR

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

AU - Ikkala, Olli T.

AU - Pietilä, Lars-Olof

AU - Ahjopalo, Lisbeth

AU - Österholm, Heidi

AU - Passiniemi, Pentti J.

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.

KW - electrically conducting polymer

KW - hydrogen bonding

KW - molecular recognition

KW - phenyl-phenyl interaction

KW - solvent

KW - electrically conducting polymer

KW - hydrogen bonding

KW - molecular recognition

KW - phenyl-phenyl interaction

KW - solvent

KW - electrically conducting polymer

KW - hydrogen bonding

KW - molecular recognition

KW - phenyl-phenyl interaction

KW - solvent

UR - http://www.scopus.com/inward/record.url?scp=36449003505&partnerID=8YFLogxK

U2 - 10.1063/1.469952

DO - 10.1063/1.469952

M3 - Article

VL - 103

SP - 9855

EP - 9863

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 22

ER -

ID: 4685113