Nanoscale conducting cylinders based on self-organization of hydrogen-bonded polyaniline supramolecules Kosonen, H.; Ruokolainen, J.; Knaapila, M.; Torkkeli, M.; Jokela, K.; Serimaa, R.; ten Brinke, G.; Bras, W.; Monkman, A.P.; Ikkala, O.ABSTRACT: Comb-shaped or hairy rodlike supramolecules can be obtained by hydrogen bonding rigid rod polymers and amphiphilic oligomers. Here we introduce a concept to achieve electrically conducting acid doped PANI to allow cylindrical self-organization. PANI is doped with camphorsulfonic acid (CSA) where 4-hexylresorcinol (Hres) is hydrogen bonded to form supramolecules, which further undergo selforganization. The structure formation of PANI(CSA) 0.5(Hres)y complexes is discussed on the basis of smalland wide-angle X-ray scattering and electrical conductivity. Highly ordered hexagonal cylindrical structures were observed with a distance between the cylinders around 35 Å. Electrical conductivity increases 2 orders of magnitude upon formation of cylindrical structures, potentially due to confinement of PANI chains within the cylinders. The method would then allow an easy preparation of nanoscale organic conducting wires, just by mixing the components together.
Deposited in DRO:PW tnury PHIS Version of attached le: ulished ersion Peer-review status of attached le: eerEreviewed Citation for published item: unpilD wF nd skklD yF nd orkkeliD wF nd tokelD uF nd erimD F nd holnyD sFF nd frsD F nd ten frinkeD qF nd rorsurghD vFiF nd ¦ lssonD vFEyF nd wonkmnD eFF @PHHPA 9olrized luminesene from selfEssemledD lignedD nd leved suprmoleules of highly ordered rodlike polymersF9D epplied physis lettersFD VI @VAF ppF IRVWEIRWIF Further information on publisher's website: httpsXGGdoiForgGIHFIHTQGIFIRWWPPP Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. A hierarchical self-assembly in comb-shaped supramolecules of conjugated rodlike polymers is reported. The supramolecules consist of poly͑2,5-pyridinediyl͒, acid dopants, and hydrogen bonded alkyl side chains. A thermotropic smectic state with an exceptionally large coherence length is formed without additional solvent. This allows facile overall alignment resulting in high dichroism and polarized photoluminescence. Solid films are formed by cleaving side groups from the supramolecules which retain the optical anisotropy together with the high photoluminescence quantum yield of pristine polymer.
Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte Citation for published version (APA): Kosonen, H., Valkama, S., Hartikainen, J., Eerikainen, H., Torkkeli, M., Jokela, K., ... Eerikäinen, H. (2002). Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte. Macromolecules, 35(27), ABSTRACT: We report self-organized polymer electrolytes based on poly(styrene)-block-poly(4-vinylpyridine) (PS-block-P4VP). Liquidlike ethylene oxide (EO) oligomers with sulfonic acid end groups are bonded to the P4VP block, leading to comb-shaped supramolecules with the PS-block-P4VP backbone. Lithium perchlorate (LiClO 4) has been added to the EO-rich domains. Small-and wide-angle X-ray scattering in combination with Fourier transformation infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), ac impedance, and dynamic mechanical spectroscopy (DMA) suggests alternating lamellae of reinforcing glassy PS domains and ionically conducting "nanochannels" consisting of poly(4-vinylpyridinium), oligomeric ethylene oxide sulfonates, and LiClO 4. The long period of the self-organization is ca. 300 Å. So far, the ionic conductivity levels remained relatively low, i.e., 10 -7 -10 -6 S/cm at room temperature and 10 -5 -10 -4 S/cm at 80°C. However, as self-organization of polymeric supramolecules allows combining glassy reinforcing domains and well-plasticized domains consisting of oligomers with high segmental motions, there may exist possibilities to tune feasible combination of electrical and mechanical properties.
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