Molecular recognition solvents for electrically conductive polyaniline

T. Vikki, Lars-Olof Pietilä, Heidi Österholm, Lisbeth Ahjopalo, A. Takala, A. Toivo, K. Levon, Pentti Passiniemi, Olli Ikkala (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

97 Citations (Scopus)

Abstract

Due to its semirigid nature, electrically conductive polyaniline (PANI) has long been regarded as an intractable material, i.e. infusible and poorly soluble in organic compounds. Among the rare exceptions is camphorsulfonic acid (CSA) doped PANI, which exhibits good solubility in m-cresol, whereas for other sulfonic acid dopants (e.g. dodecylbenzenesulfonic acid (DBSA)) the solubility in common solvents is poor. We report exceptionally high solubility of fully DBSA and CSA protonated PANI in a crystalline compound, 1,3-dihydroxybenzene, i.e. resorcinol. Up to 20−30 wt % of PANI(DBSA)0.5 and PANI(CSA)0.5 can be dissolved in resorcinol at 200−220 °C to form particle-free films as observed by optical microscopy. High PANI complex concentrations require high temperatures for dissolution, suggesting UCST behavior with a high critical temperature. Optical microscopy, calorimetry, and X-ray analysis suggest that the solution initially is amorphous. With time, crystallinity develops within the sample, due to partial phase separation of resorcinol while part of it remains miscible. Calculations show that a resorcinol molecule is able to simultaneously form two hydrogen bonds and one phenyl/phenyl interaction with the PANI/sulfonic acid complex, because of their steric match. The conditions required to achieve such matching interactions, i.e. molecular recognition, are discussed. The concept can be extended to find a large category of novel solvents for electrically conductive PANI to yield soluble and fusible complexes.
Original languageEnglish
Pages (from-to)2945-2953
Number of pages9
JournalMacromolecules
Volume29
Issue number8
DOIs
Publication statusPublished - 1996
MoE publication typeA1 Journal article-refereed

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Molecular recognition
Polyaniline
Acids
Sulfonic Acids
Solubility
Optical microscopy
polyaniline
X ray analysis
Calorimetry
Organic compounds
Phase separation
Hydrogen bonds
Dissolution
Doping (additives)
Crystalline materials
Temperature
Molecules
resorcinol

Cite this

Vikki, T., Pietilä, L-O., Österholm, H., Ahjopalo, L., Takala, A., Toivo, A., ... Ikkala, O. (1996). Molecular recognition solvents for electrically conductive polyaniline. Macromolecules, 29(8), 2945-2953. https://doi.org/10.1021/ma951555v
Vikki, T. ; Pietilä, Lars-Olof ; Österholm, Heidi ; Ahjopalo, Lisbeth ; Takala, A. ; Toivo, A. ; Levon, K. ; Passiniemi, Pentti ; Ikkala, Olli. / Molecular recognition solvents for electrically conductive polyaniline. In: Macromolecules. 1996 ; Vol. 29, No. 8. pp. 2945-2953.
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Vikki, T, Pietilä, L-O, Österholm, H, Ahjopalo, L, Takala, A, Toivo, A, Levon, K, Passiniemi, P & Ikkala, O 1996, 'Molecular recognition solvents for electrically conductive polyaniline', Macromolecules, vol. 29, no. 8, pp. 2945-2953. https://doi.org/10.1021/ma951555v

Molecular recognition solvents for electrically conductive polyaniline. / Vikki, T.; Pietilä, Lars-Olof; Österholm, Heidi; Ahjopalo, Lisbeth; Takala, A.; Toivo, A.; Levon, K.; Passiniemi, Pentti; Ikkala, Olli (Corresponding Author).

In: Macromolecules, Vol. 29, No. 8, 1996, p. 2945-2953.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Molecular recognition solvents for electrically conductive polyaniline

AU - Vikki, T.

AU - Pietilä, Lars-Olof

AU - Österholm, Heidi

AU - Ahjopalo, Lisbeth

AU - Takala, A.

AU - Toivo, A.

AU - Levon, K.

AU - Passiniemi, Pentti

AU - Ikkala, Olli

PY - 1996

Y1 - 1996

N2 - Due to its semirigid nature, electrically conductive polyaniline (PANI) has long been regarded as an intractable material, i.e. infusible and poorly soluble in organic compounds. Among the rare exceptions is camphorsulfonic acid (CSA) doped PANI, which exhibits good solubility in m-cresol, whereas for other sulfonic acid dopants (e.g. dodecylbenzenesulfonic acid (DBSA)) the solubility in common solvents is poor. We report exceptionally high solubility of fully DBSA and CSA protonated PANI in a crystalline compound, 1,3-dihydroxybenzene, i.e. resorcinol. Up to 20−30 wt % of PANI(DBSA)0.5 and PANI(CSA)0.5 can be dissolved in resorcinol at 200−220 °C to form particle-free films as observed by optical microscopy. High PANI complex concentrations require high temperatures for dissolution, suggesting UCST behavior with a high critical temperature. Optical microscopy, calorimetry, and X-ray analysis suggest that the solution initially is amorphous. With time, crystallinity develops within the sample, due to partial phase separation of resorcinol while part of it remains miscible. Calculations show that a resorcinol molecule is able to simultaneously form two hydrogen bonds and one phenyl/phenyl interaction with the PANI/sulfonic acid complex, because of their steric match. The conditions required to achieve such matching interactions, i.e. molecular recognition, are discussed. The concept can be extended to find a large category of novel solvents for electrically conductive PANI to yield soluble and fusible complexes.

AB - Due to its semirigid nature, electrically conductive polyaniline (PANI) has long been regarded as an intractable material, i.e. infusible and poorly soluble in organic compounds. Among the rare exceptions is camphorsulfonic acid (CSA) doped PANI, which exhibits good solubility in m-cresol, whereas for other sulfonic acid dopants (e.g. dodecylbenzenesulfonic acid (DBSA)) the solubility in common solvents is poor. We report exceptionally high solubility of fully DBSA and CSA protonated PANI in a crystalline compound, 1,3-dihydroxybenzene, i.e. resorcinol. Up to 20−30 wt % of PANI(DBSA)0.5 and PANI(CSA)0.5 can be dissolved in resorcinol at 200−220 °C to form particle-free films as observed by optical microscopy. High PANI complex concentrations require high temperatures for dissolution, suggesting UCST behavior with a high critical temperature. Optical microscopy, calorimetry, and X-ray analysis suggest that the solution initially is amorphous. With time, crystallinity develops within the sample, due to partial phase separation of resorcinol while part of it remains miscible. Calculations show that a resorcinol molecule is able to simultaneously form two hydrogen bonds and one phenyl/phenyl interaction with the PANI/sulfonic acid complex, because of their steric match. The conditions required to achieve such matching interactions, i.e. molecular recognition, are discussed. The concept can be extended to find a large category of novel solvents for electrically conductive PANI to yield soluble and fusible complexes.

U2 - 10.1021/ma951555v

DO - 10.1021/ma951555v

M3 - Article

VL - 29

SP - 2945

EP - 2953

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 8

ER -

Vikki T, Pietilä L-O, Österholm H, Ahjopalo L, Takala A, Toivo A et al. Molecular recognition solvents for electrically conductive polyaniline. Macromolecules. 1996;29(8):2945-2953. https://doi.org/10.1021/ma951555v